Understanding the Schrödinger Equation

Contents
1 Schrödinger Equation (1-D) 11

1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.1.1 Importance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.1.2 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.1.3 Natural Units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.2 General properties of the Schrödinger Equation . . . . . . . . . . . . . . . . . . . . . . 16
1.2.1 Linearity, Superposition principle . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.2.2 Time Independent Schrödinger Equation . . . . . . . . . . . . . . . . . . . . . . 16
1.2.3 Boundary Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.2.4 Interpretation, Probability conservation . . . . . . . . . . . . . . . . . . . . . . 17
1.2.5 Expected values, Momentum space, Eigenvalues and Dirac Notation . . . . . . 17
1.2.6 Heisenberg Uncertainty principle . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.2.7 Correspondence Principle and Ehrenfest Theorem . . . . . . . . . . . . . . . . 18
1.3 Simple Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.3.1 Free Particle (Plane Wave) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.3.2 Step Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.3.3 Potential Barrier (Ramsauer and Tunnel effects) . . . . . . . . . . . . . . . . . 26
1.3.4 Infinite Potential Well . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
1.3.5 Finite Potential Well . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.4 Harmonic oscillator (1-D) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.5 Exercises, Schrödinger Equation (1-D) . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
1.5.1 Matter waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
1.5.2 Other wells and steps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
1.5.3 Infinite well . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
1.5.4 Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
1.5.5 Other Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2 Schrödinger Equation 3D 51
2.1 Center of mass motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.2 Cartesian coordinates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.2.1 Plane waves, free particle (3-D) . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.2.2 Particle in a perfect box . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.2.3 Anisotropic Harmonic oscillator (3-D) . . . . . . . . . . . . . . . . . . . . . . . 52
2.2.4 Particle in a Magnetic Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
2.3 Central Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
1
2 CONTENTS
2.3.1 Spherical Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

2.3.2 Infinite spherical bag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2.3.3 Finite spherical bag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
2.3.4 Isotropic harmonic oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.3.5 Coulomb potential, Hydrogenic atoms . . . . . . . . . . . . . . . . . . . . . . . 60
2.4 Schrödinger Eq. (3D) exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2.4.1 CM motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2.4.2 Cartesian coordinates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2.4.3 Central Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
2.4.4 Hydrogenic atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3 Quantum Mechanics Formalism 71

3.1 Mathematical framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.1.1 Hilbert Spaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.1.2 Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.1.3 Representations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.2 Quantum Mechanics Formalism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.2.1 Postulate I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.2.2 Postulate II . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.2.3 Postulate III . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.2.4 Postulate IV, Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.3 Interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.3.1 Copenhagen Interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.3.2 Other interpretations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.3.3 ‘Paradoxes’ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.4 Selected Phenomenology, interpretation and applications . . . . . . . . . . . . . . . . . 86
3.4.1 Bell inequalities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.4.2 Quantum Computing, Chriptography, Teleprotation, etc . . . . . . . . . . . . . 87
3.4.3 Transition from Quantum to Classical Physics . . . . . . . . . . . . . . . . . . 89
3.4.4 Historical quotations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.5 Formalism, exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.6 Quantum Mechanics Interpretation references . . . . . . . . . . . . . . . . . . . . . . . 95
4 Angular Momentum 101

4.1 Orbital Angular Momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4.1.1 Orbital Angular Momenta eigenvalues and Spherical harmonics . . . . . . . . . 102
4.2 Angular Momenta, General case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4.2.1 Rotations group: SU (2) algebra . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4.2.2 Irreducible Representations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
4.2.3 Sum of Angular Momentun . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
4.2.4 Clebsch-Gordan Coefficients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
4.2.5 Wigner-Eckart Theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4.3 Aplications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.3.1 Raman Spectroscopy (Molecular Rotation) . . . . . . . . . . . . . . . . . . . . 113
4.3.2 Stern-Gerlach Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.3.3 Pauli Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
CONTENTS 3
4.3.4 Magnetic dipoles in magnetic fields . . . . . . . . . . . . . . . . . . . . . . . . . 119

4.3.5 Paramagnetic Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
4.3.6 NRM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
4.3.7 Electron-Spin Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4.3.8 LS and JJ Schemes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
4.4 Angular Momenta Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
4.4.1 Orbital Angular Momenta Exercises . . . . . . . . . . . . . . . . . . . . . . . . 127
4.4.2 Angular Momenta, general . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
4.4.3 Sum of Angular Momenta . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.4.4 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
4.5 Angular Momenta references . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
5 Theory of Perturbations 137

5.1 Time independent perturbations (Rayleigh-Schrödinger) . . . . . . . . . . . . . . . . . 137
5.1.1 No degenerate case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
5.1.2 Degenerate case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
5.2 Time dependent Perturbation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
5.3 Interaction Picture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
5.4 Semiclassical Aproximation (WKB Method) . . . . . . . . . . . . . . . . . . . . . . . . 142
5.4.1 Bohr-Sommerfeld Quantization rules . . . . . . . . . . . . . . . . . . . . . . . . 144
5.5 Variational principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
5.6 Numerical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
5.6.1 Time independent 1D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
5.6.2 Matrix diagonalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
5.6.3 Time dependent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
5.6.4 Scattering theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
5.6.5 Several particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.6.6 Monte Carlos, Finite Temperature . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.6.7 Path Integrals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.7 Perturbation Theory, Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
5.7.1 Perturbations time independent (non-degenerate case) . . . . . . . . . . . . . 150
5.7.2 Time independent perturbation (degenerate case) . . . . . . . . . . . . . . . . . 151
5.7.3 Time dependent perturbation theory, exercises . . . . . . . . . . . . . . . . . . 157
5.7.4 Semiclassical Approximation (WKB method) and Bohr-Sommerfeld quantiza-
tion rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
5.7.5 Variational Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
5.7.6 Numerical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6 Topics in Atomic Physics 165

6.1 Hydrogenic atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
6.1.1 Nuclei mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
6.1.2 Relativistic corrections at order (Zα)2 . . . . . . . . . . . . . . . . . . . . . . . 165
6.1.3 Case m2 > m1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
6.1.4 Lamb-Retherford shift at order α(Zα)2 . . . . . . . . . . . . . . . . . . . . . . 169
6.1.5 Case m2 = m1 = m . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
6.2 Hydrogenic atoms in external fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
4 CONTENTS
6.2.1 Zeeman effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174

6.2.2 Paschen-Back effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
6.2.3 Stark effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
6.3 Several electrons atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
6.3.1 Helium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
6.3.2 Several electrons atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
6.3.3 General Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
6.3.4 Central Potentials, Self Consistent Aproaches . . . . . . . . . . . . . . . . . . . 181
6.3.5 Periodic Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
6.3.6 LS and JJ couplings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.3.7 X rays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.3.8 External Fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.4 Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.4.1 Born-Oppenheimer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.4.2 Electronic Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.4.3 Roto-vibrational spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.4.4 Van der Walls forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.5 Exercises on Atomic Physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
6.5.1 Reduced Mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
6.5.2 General, Breit Fermi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
6.5.3 Fine Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
6.5.4 Lamb-Retherford . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
6.5.5 Hyperfine structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
6.5.6 Zeeman and Stark effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
6.6 Atomic Physics references . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
7 Radiation 195
7.1 Semiclassical radiation theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
7.1.1 Multipolar expansion, Electric and magnetic dipole approximations . . . . . . . 196
7.1.2 Absorsion of Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
7.1.3 Estimulated emision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
7.1.4 Spontaneous emision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
7.1.5 Black body radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
7.1.6 Selection rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
7.1.7 Half-life and line width. Photoelectric effect . . . . . . . . . . . . . . . . . . . . 198
7.2 Radiation exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
8 Scattering Theory 201

8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
8.2 Integral Schrödinger Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
8.2.1 Born Aproximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
8.2.2 Form Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
8.2.3 Range of validity of the Fermi’s Golden Rule . . . . . . . . . . . . . . . . . . . 204
8.3 Partial Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.3.1 Partial waves decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.3.2 Calculation of δl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
CONTENTS 5
8.4 Exact solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204

8.4.1 Hard sphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.4.2 soft sphere and Finite well . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.4.3 Rutherford case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.5 Resonances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.5.1 Resonances 1-D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.5.2 Resonances: case of finite well . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.5.3 Breit-Wigner parametrization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.6 Spin effects. Identical particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.7 Inelasticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
8.7.1 Optical Theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
8.8 S-Matrix properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
8.9 Lippman-Schwinger Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
8.10 Approximate Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
8.11 Scattering Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
8.11.1 Born’s Approximation Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . 206
8.11.2 Partial Wave Phases, Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
8.11.3 Exact solutions, Resonances and Inelasticity Exercises . . . . . . . . . . . . . . 207
9 Path or Feynman Integrals 209

9.1 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
9.1.1 Schrödinger representation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
9.1.2 Spatial and momentum representations . . . . . . . . . . . . . . . . . . . . . . 209
9.1.3 Path or Feynman integrals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
9.1.4 Example: Free particle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
9.1.5 Example: harmonic oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
9.1.6 Path Integral properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
9.1.7 Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
9.1.8 Expectation values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
9.2 Semiclassical Approximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
9.2.1 Example: the harmonic oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . 214
9.3 Quantum Fields: Scalars, Fermions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
9.4 Perturbation Theory. Feynmann diagrams. . . . . . . . . . . . . . . . . . . . . . . . . 214
9.5 Loop expansion. Effective potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
10 QM References 215
10.1 Basic References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
10.2 Complemetary math. references . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
10.3 Matter Waves references . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
10.4 Perturbative solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
10.5 Semiclassical theory of Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
10.6 Scattering Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
10.7 Relativistic Quantum Mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
10.8 Feynman Integrals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
6 CONTENTS
A Constants and Formulae 227

A.1 Constants, units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
A.2 Useful formulae 1-D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
A.3 Useful formulae 3-D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
A.4 Formalism formulae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
A.5 Angular Momenta . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
A.6 Perturbations theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
A.7 Matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
A.8 Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
A.9 Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
A.10 Integrals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
B Math 233
B.1 Basic Math . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
B.1.1 Trigonometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
B.1.2 Quadratic (Conic) Plots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
B.1.3 Vectorial Calculus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
B.1.4 Curvilinear coordinates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
B.1.5 Dirac’s delta . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
B.1.6 Complex Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
B.1.7 Analytical Integrals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
B.1.8 Relativity and Tensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
B.2 Special Functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
B.2.1 Bessel functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
B.2.2 Spherical Bessel functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
B.2.3 Hypergeometric functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
B.2.4 Confluent Hypergeometric functions . . . . . . . . . . . . . . . . . . . . . . . . 239
B.2.5 Airy Function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
B.2.6 Polylogarithmic functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
B.2.7 Error, Fresnel and related functions . . . . . . . . . . . . . . . . . . . . . . . . 242
B.3 Polynomials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
B.3.1 Legendre Polynomials and functions . . . . . . . . . . . . . . . . . . . . . . . . 242
B.3.2 Spherical harmonics and Angular Momenta . . . . . . . . . . . . . . . . . . . . 245
B.3.3 Gegenbauer Polynomials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
B.3.4 Chebyshev Polynomials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
B.3.5 Laguerre Polynomials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
B.3.6 Hermite Polynomials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
B.4 Numerical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
B.4.1 Gaussian Integration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
B.4.2 Singular integrals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
B.4.3 Fitting data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
B.5 Math exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
List of Tables
6.1 Main contributions to the energy splitting of the 2s1/2 and 2p1/2 . . . . . . . . . . . . 170
6.2 Lamb shift for hydrogen and other elements [Lamb] . . . . . . . . . . . . . . . . . . . . 171
6.3 Hyperfine splitting for hydrogen and other elements. . . . . . . . . . . . . . . . . . . . 171
6.4 2S − 1S transitions. * rd2 − rp2 = 3.8212(15) fm2 [Lamb] . . . . . . . . . . . . . . . . . 171
6.5 Ps transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
7
8 LIST OF TABLES
List of Figures
1.1 Old phenomenology, unexplained by Classical Physics: discrete spectra, black body
radiation laws, photoelectric effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2 Quantum Mechanics hagiography: Plank, Einstein, Bohr, Sommerfeld, De Broglie,
Schrödinger, Heisenberg, Born, Compton, Dirac, Feynman, etc . . . . . . . . . . . . . 14
1.3 Real measurement. The results can be plotted as histograms. In this case for KS → 2π
and Z → e− e+ . M 2 = E 2 − p2 = (E1 + E2 )2 − (p1 + p2 )2 . . . . . . . . . . . . . . . . 19
1.4 Electron diffraction: a) by a crystal (Davisson-Germer 1927) b) by crystals in powder
(G. Thomson 1927) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.5 Two-slit electron interference and diffraction: One by one n=1, 10, 1000 electrons,
Jönson 1961 [7]. Electron and positron as particles of defined trajectories. Neutrons
diffraction single slit, Zeilinger. Neutron interference pattern for a double slit. Zeilinger. 23
1.6 Time evolution of a wavepacket. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.7 : Transmission and reflection coefficients for the rectangular potential step . . . . . . . 25
1.8 Transmission and reflection coefficients for the rectangular potential barrier. Ramsauer
and Tunnel effect . Negative resistance in he tunnel diode. . . . . . . . . . . . . . . . . 27
1.9 Scanning tunnelling microscope (STM) picture of a stadium-shaped ”quantum corral”
made by positioning iron atoms on a copper surface. This structure was designed for
studying what happens when surface electron waves in a confined region. Courtesy,
Don Eigler, IBM. Quantum Mirage: A STM microscope was used to position 36 cobalt
atoms in an elliptical quantum corral. Electron waves moving in the copper substrate
interact both with a magnetic cobalt atom carefully positioned at one of the foci of the
ellipse and apparently with a ”mirage” of another cobalt atom (that isn’t really there)
at the other focus. (Courtesy of IBM.) reported by: Manoharan et al., in Nature, 3 Feb.
2000 Electron Waves in a Plane: In this scanning tunneling microscope (STM) image,
electron density waves are seen to be breaking around two atom-sized defects on the
surface of a copper crystal. The resultant standing waves result from the interference
of the electron waves scattering from the defects. Courtesy, Don Eigler, IBM. ADN . . 29
1.10 Finite width potential barrier. T as a function of x for c = 1, 10, and 50. Numerical
solution to eq. (1.40) for the same values of c. . . . . . . . . . . . . . . . . . . . . . . . 31
1.11 Harmonic oscillator wavefunctions for several the ground and several exited states . . 33
1.12 Figures corresponding to the 1D exercises. Colella experiment. semi-infinite well. Sym-
metric finite well. Odd and even wave function. Two semi-harmonic oscillator well.
Dirac’s comb. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.1 ‘Perfect’ spherical bag spectra 2µa2 Enl = x2nl , with n2S+1 LJ . . . . . . . . . . . . . . . 56
9
10 LIST OF FIGURES
2.2 Finite spherical bag spectra Enl /V0 , with c = 15 and n2S+1 LJ . . . . . . . . . . . . . . 58
2.3 Isotropic harmonic oscillator spectra Enl = (2n + l + 3/2)ω, with n2S+1 LJ . . . . . . . 59
2.4 Hydrogenic atoms spectra 2Enl /µ(Zα)2 . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.1 Quamtum jumps [Bell]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82

3.2 Bell inequalities violation [Bell]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4.1 An infinitesimal rotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102

4.2 Clebsh-Gordan coefficients. Taken from PDG at wwww.lbl.gov . . . . . . . . . . . . . 111
4.3 Raman spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.4 Stern-Gerlach experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.5 NRM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.1 Figures for the Perturbation theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138

5.2 Geiger-Nuttal law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
5.3 Figures for the exercises of Perturbation theory . . . . . . . . . . . . . . . . . . . . . . 152
6.1 Schematic representation of the energy levels of hydrogenic atoms, in the Bohr’s, Fine
structure, Lamb shift, hyperfine energy approximations. n2S+1 LJ . . . . . . . . . . . . 169
6.2 Positronium and Bottonium energy levels comparison. Notice the energies involved.
n2S+1 LJ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
Chapter 1
Schrödinger Equation (1-D)
1.1 Introduction
1.1.1 Importance
Quantum Mechanics has been the base of many developments and applications in Physics and in the
Industry in the XX century.
1. Basic science: The Standard Model of elementary particles (involving 3 of the 4 known in-
teractions: Electromagnetic, Weak and Strong) is based in Quantum Mechanics. The other
interaction, the gravity we know is not complete because nobody has been able to obtain a
consistent theory of Quantum Gravity. Even ‘exotic’ theories like SUSY, GUT, Superstrings
and so on involve QM.
2. At the moment all the experiments realized are consistent with QM predictions (including the
Bohr’s interpretations). In many case with very high accuracy like in Quantum Electrodynamics
with Quantum Optics, maybe the better known fields or all sciences.
3. Quantum Mechanics (together with Electromagnetism, Statistical Mechanics, etc.) is the basic
theory for many areas in Physics and Science. Such is the case of Condensed Matter, Atomics
and Molecular Physics, Chemistry, Materials Science, Nuclear Physics, Particle Physics, Optics
and many more.
4. Many inventions have been possible thanks to Quantum Mechanics, like Lasers, Computers
(transistors, integrated circuits), advances in communications, new materials and so on.
1.1.2 History
A short review of the most important developments related to Quantum Mechanics may be like
[QM history]:
1. -480 Pythagoras discover the law for vibrating strings, involving integer numbers. Vibrating
frequencies are quantized!.
2. -420 Zeno of Elea denounces his paradoxes, involving irrational numbers. The continuous.
11
12 CHAPTER 1. SCHRÖDINGER EQUATION (1-D)
Figure 1.1: Old phenomenology, unexplained by Classical Physics: discrete spectra, black body radi-
ation laws, photoelectric effect
3. 1666 Newton discover spectra. He postulated that light is composed by particles of different
size: smaller the violet and larger the red. This is why blue light is easily refracted [Optiks,
Query 29]
4. 1752 T. Melvill observed by the first time spectral lines.
5. 1802 W. Wollaston discovers dark lines in the solar spectra.
6. 1803 Dalton introduces the atomic hypothesis to explain the proportionality law of chemical
reactions.
7. 1814 Fraunhofer discovers dark lines in the solar spectra and study them.
8. 1815, circa. P. Laplace (1749-1827): ‘An intellect which at any given moment knows all the forces
that animate Nature and the mutual positions of the beings that comprise it, if this intellect were
vast enough to submit its data to analysis, could condense into a single formula the movement
of the greatest bodies of the universe and that of the lightest atom: for such an intellect nothing
could be uncertain; and the future just like the past would be present before its eyes’
9. 1835, Auguste Comte, the French philosopher and founder of sociology, said of the stars: We
shall never be able to study, by any method, their chemical composition or their mineralogical
structure... Our positive knowledge of stars is necessarily limited to their geometric and mechan-
ical phenomena
10. 1860-s Chemists (Gay Lussac, Avogadro, Canizzaro, etc.) adopt the atomic hypothesis
11. 1859 G. Kirchhoff discovers its black body radiation formula. He enounces the principle that
spectra is the ‘fingerprint’ of each element.
1.1. INTRODUCTION 13
12. 1868-70 Mendeleiev Periodic Table.
13. 1879 J. Stefan, 1884 L. Boltzmann find the so called Stefan-Boltzmann black body radiation
formula.
14. 1885 J. Balmer, discover his mathematical formula for hydrogen. J. Rydberg 1888, Ritz, etc.
extended it.
15. 1886-7 H. Hertz discovers the photoelectric effect.
16. 1896 W. Wein discovers his law, that fails for short wavelenghts. X-rays (Rötger), Radioactivity
(Curie-Bequerel)
17. 1897 e− is discovered by J. J. Thomson. Atomic structure (hypothesis) (Thomson): ‘plum

pudding’ atomic Model. Zeeman effect.
18. 1894-1900. Classical Physics:
(a) L. Kelvin at speech British Association for the Advancement of Science 1900: ‘There is
nothing new to be discovered now. All that remains is more and more precise measurement’.
(b) On 27th April 1900, Lord Kelvin gave a lecture to the Royal Institution of Great Britain.
The title of the lecture was ‘Nineteenth-Century Clouds over the Dynamical Theory of Heat
and Light’. Kelvin mentioned, in his characteristic way, that the ‘beauty and clearness
of theory was overshadowed by ‘two clouds’. He was talking about the null result of the
Michelson-Morley experiment and the problems of blackbody radiation.
(c) Mechanics and EM. A. Michelson, from his address at the dedication ceremony for the
Ryerson Physical Laboratory at the University of Chicago: ‘The more important funda-
mental laws and facts of physical science have all been discovered, and these are now so
firmly established that the possibility of their ever being supplanted in consequence of new
discoveries is exceedingly remote.... Our future discoveries must be looked for in the sixth
place of decimals’. A. Michelson and ‘Light waves and their uses 1903.
19. 1900 Quantum Mechanics (Planck), ~. By combining the formulae of Wien and Rayleigh, Planck
announced in October 1900 a formula now known as Planck’s radiation formula. Within two
months Planck made a complete theoretical deduction of his formula renouncing classical physics
and introducing the quanta of energy. On 14 December 1900 he presented his theoretical expla-
nation involving quanta of energy at a meeting of the Physikalische Gesellschaft in Berlin. In
doing so he had to reject his belief that the second law of thermodynamics was an absolute law
of nature, and accept Boltzmann’s interpretation that it was a statistical law. In a letter written
a year later Planck described proposing the theoretical interpretation of the radiation formula
saying: ‘... the whole procedure was an act of despair because a theoretical interpretation had
to be found at any price, no matter how high that might be’.
20. 1901 Radioactive decays are founded to be of statistical nature.
21. 1905 Relativity and Photoelectric effect (Einstein), ~ again.
22. 1909 G. Taylor. Double slit experiment with photons. Statistical (QM) behavior
Figure 1.2: Quantum Mechanics hagiography: Plank, Einstein, Bohr, Sommerfeld, De Broglie,
Schrödinger, Heisenberg, Born, Compton, Dirac, Feynman, etc
23. 1911 Atomic Structure (Rutherford). Nucleus and electrons .
24. 1913 Quantum Mechanics applied to atomic spectra (Bohr), still the same ~!. Stark discovers
his effect.
25. 1914 Frank-Hertz experiment.
26. 1917 Einstein talks about the statistical nature of the direction at which photons are emitted
spontaneously .
27. 1918 Quantum Mechanics and Relativity applied to atomic spectra (Sommerfeld).
28. 1920 Ramsauer effect, discovered by Ramsauer and Townsend.
29. 1923 Matter waves (De Broglie)[7]. Compton discovers the ‘photon’.
30. 1924 Bose-Einstein statistics and Identical particles.
31. 1925 S. Goudsmit and U. Uhlenbeck propose spin .
32. 1926 Quantum Mechanics Dynamics (Schrödinger and Heisenberg ). Semiclassical radiation
theory (Heisenberg). Statistical nature of the wave function : ‘determinism of classical physics
turns out to be an illusion, created by overrating mathematico-logical concepts. It is an idol, not
an ideal in scientific research and cannot, therefore, be used as an objection to the essentially
indeterministic statistical interpretation of quantum mechanics’ (M. Born at the Nobel Speech
in 1954).
33. 1927 e− -wave : Davisson-Germer and G. Thomson 30-s. Heisenbeg’s uncertainty principle . EM
quantization : Dirac, Heisenberg ; Pauli, Jordan, etc. Explanation of Spontaneous emission by
QFT .
1.1. INTRODUCTION 15
34. 1928 Theoretical (tunnel effect ’colorblack) explanation of the α decay (Strong Interactions ).
Gamow, Condon and Guney.
35. 1931 E. Ruska and M. Kroll. First Transmission Electron Microscope (TEM).
36. 1930-s Bohr-Einstein debate on the Quantum Mechanics Interpretation.
37. 1932 Dirac Equation : QM, Relativity Spin and Classical EM. It predicts antimatter . J. von
Neumann develops the mathematical framework of Quantum Mechanics.
38. 1933 Anderson discovers pair production and the positron : γ → e− e+
39. 1934 Fermi, first QFT of Weak Interactions .
40. 1935 Yukawa , first QFT of Strong Interactions.
41. 1947 Transistor . Bardeen, Brattain.
42. 1949 Lamb-Retherford experiment. EM fields are quantized too.
43. 1954 C. Townes and A. Schawlow invented the maser
44. 1950-s QED Theory by Tomonaga, Feynmann, Schwinger, etc. to explain the Lamb-Retherford
experiment. Quantum Field Theory. Renormalization.
45. 1958. J. Kilby. Integrated circuits. Lasers, C. Townes and A. Schawlow
46. 1961 Jönson two slits experiment with electrons.
47. 1963 Feynman on two slits experiment: ‘We choose to examine a phenomenon which is impos-
sible, absolutely impossible, to explain in any classical way, and which has in it the heart of
quantum mechanics. In reality, it contains the only mystery. We cannot make the mystery go
away by explaining how it works . . . In telling you how it works we will have told you about
the basic peculiarities of all quantum mechanics’.
48. 1968-73 Weinberg-Salam Model: Weak interactions theory, QM, EM and Relativity
49. 1974 QCD. Quantum Chromodynamics: Strong Interactions, QM and Relativity.
50. 1981 STM (Scanning Tunneling Microscope). G. Binnig and H. Rohrer. Experimental test of
Bell inequalities (A. Aspect), favorable to Bohr’s interpretation.
51. 1995 BEC (Bose-Einstein condensate). E. Cornell, W. Ketterle and C. Wieman.
1.1.3 Natural Units

1. In this notes I’m going to use ‘Natural Units’, that’s it ~ = c = 1.
2. Thus the fundamental units can be taken as energy and electric charge.
3. [T ] = [L] = eV−1 . Space and time have the same units (Relativity)
4. [E] = [m] = [M ] = [ω] = [p] = [k] = eV. Energy and frequency (and so on) have the same units,
inverse length or time. Consequence of QM, like the Heisenberg uncertainly principle.
1.2 General properties of the Schrödinger Equation

A simple ‘deduction’ of the Schrödinger Equation can goes as follows: For a plane wave (free particle)
one has that ψ = A exp[i(kx − ωt)] with p = k, E = ω = p2 /2m = k 2 /2m, so ψ satisfy the Schrödinger
equation
2
∂ p 1 ∂2
Eψ = i ψ = + V (x) ψ = − + V (x) ψ (1.1)
∂t 2m 2m ∂x2
1.2.1 Linearity, Superposition principle

P
The Schrödinger Equation is linear, so a linear combination of solutions ψ = i αi ψi is a new solution,
given that all the ψi are solutions. Another name of the linearity property is the superposition principle.
Notice this condition does not hold for macroscopic collisions, for example.
1.2.2 Time Independent Schrödinger Equation

In the case the Potential energy is time independent the Schrödinger equation is separable:
1. its solutions can be written as Ψ(t, x) = φ(t)ψ(x).
(a) This general solution can be replaced into the Schrödinger Equation to obtain that
1 ∂2 ∂
Eψ = [− + V (x)]ψ = H(x)ψ, i φ(t) = Eφ(t) (1.2)
2m ∂x2 ∂t
(b) The first is the Time independent Schrödinger Equation, and the second describes the time
dependence that can be obtained easily to have the general solution as
Ψ(t, x) = ψ(x) exp[−iEt] (1.3)
2. Given than in general the Time independent admits many solutions:
H(x)ψn (x) = En ψn (x) (1.4)
3. and using the superposition principle one has that the general solution can be written as
X
Ψ(t, x) = an exp[−iEn t]ψn (x) (1.5)
n
4. Given that most of the potentials are time independent our main task is to find out all the
solutions to the Time independent Schrödinger Equation one use eq. (1.5) to have the general
time evolution of the complete solution.
1.2. GENERAL PROPERTIES OF THE SCHRÖDINGER EQUATION 17
1.2.3 Boundary Conditions

The general Boundary conditions are
1. If the potential (continuous or not) is finite the wavefunction and its derivative are continuous.
2. If the potential has an infinite discontinuity the wavefunction is continuous but not its derivative.
3. To show that let us integrate the Schrödinger Equation between x − and x + to have
Z x+
0 0
ψ (x + ) − ψ (x − ) = 2m dx (V − E)ψ ∼ [2m(V − E)ψ]x+/2 − [2m(V − E)ψ]x−/2
x−
= lim [2mV ψ]x+/2 − [2mV ψ]x−/2 (1.6)
→0
(a) If the wavefunction is discontinuous, its derivative gets a higher order discontinuity (a
Dirac’s delta) and it is not possible to satisfy the SE at x. Therefore the wavefunction is
continuous even if the potential is not.
(b) If the potential is finite on both sides of x the right side vanishes when → 0 and ψ 0 is
continuous.
(c) If the potential is not finite on at least one side the right hand side is not defined and ψ 0 is
discontinuous.
1.2.4 Interpretation, Probability conservation

1. According to Bohr’s interpretation (Copenhagen school) the density of probability is given by
ρ = |ψ|2 .
2. It can be shown that it obeys a continuity equation and it is conserved (for a real potential
energy):
∂ρ ∂ψ ∂ψ ∗ i i
= ψ∗ +ψ = [ψ ∗ ∇2 ψ − ψ∇2 ψ ∗ ] − i(V − V ∗ )ρ = ∇ · [ψ ∗ ∇ψ − ψ∇ψ ∗ ]
∂t ∂t ∂t 2m 2m
∂ρ i 1
= −∇ · J, J = [ψ∇ψ ∗ − ψ ∗ ∇ψ] = Im[ψ ∗ ∇ψ] (1.7)
∂t 2m m
3. thus for V ∗ = V probability is conserved.

R 3
4. For a bounded particle the wave function can be normalized to one: d xρ = 1 and this
normalization is maintained as time evolves, given that the continuity equation holds.
1.2.5 Expected values, Momentum space, Eigenvalues and Dirac Notation

1. According to the Bohr’s interpretation dynamical variables of Classical Physics are substituted
in Quantum Mechanics by operators: O = x, H (the energy), p = −i∇, etc.
2. In the case one measures them the result is one of the eigenvalues of the operator, λn ) (Oψn =
λn ψn ).
3. For the general case QM (the Schrödinger Equation) can only predict the expectation value, and
higher momenta of the operators, that can be compared with the respective expectation value
of the repetitive measurement
R P
d3 xψ ∗ Oψ n Nn λn
< O >QM ≡ R 3 ↔< O >exp. ≡ P (1.8)
d x|ψ| 2
n Nn
where Nn is the number of times λn is obtained in the measurements.

4. This is shown for two particular cases in the histograms of the fig. 1.3.
P
5. In general when the system is in the state ψ = n an ψn one obtains
P 2
n |an | λi
< O >QM ≡ P 2
(1.9)
i |an |
6. so the predicted probability

P of been in the state ψn (and therefore of obtain λn , when measuring
O) if one has ψ is |an |2 / i |an |2 = |an |2 if the state is normalized to one.
7. Notice that in the particular case we have an eigenstate, ψn the prediction is that one measures
λn with probability one!.
1.2.6 Heisenberg Uncertainty principle

1. In general for all waves is valid that ∆k∆x ≥ 1
p p
2. ∆f ≡ ∆frms ≡ h(f − < f >)2 i = < f 2 > − < f >2
3. Matter waves are not the exception and one has that
∆p∆x ≥ 1 (1.10)
4. so it is not possible to know simultaneously the position and the momenta of a given particle
with an accuracy greater than that given by eq. (1.10)
1.2.7 Correspondence Principle and Ehrenfest Theorem

Quantum Mechanics becomes Classical Mechanics when
1. a typical Action (A ' pR) is much more greater that ~.

2. This was enounced by Bohr as the Correspondence Principle.
3. it is guarantied by the Ehrenfest Theorem (1927):
d<x> 1 d
= , = − < ∇V > (1.11)
dt m dt
1.3. SIMPLE POTENTIALS 19
Figure 1.3: Real measurement. The results can be plotted as histograms. In this case for KS → 2π
and Z → e− e+ . M 2 = E 2 − p2 = (E1 + E2 )2 − (p1 + p2 )2
4. Decoherent waves becomes Classical Physics
Wave particle
Quantum Classical
Schrödinger E. Minimal Action
Wave Eq. Fermat Principle
Physical Optics Geometrical Optics
1.3 Simple Potentials

1.3.1 Free Particle (Plane Wave)
In this case the Schrödinger Equation becomes, and its solution
1 ∂2 ∂
Hψ = − ψ(x) = i ψ
2m ∂x2 ∂t
ψ = Aei(kx−ωt) (1.12)
1. with ω = E = k 2 /2m = p2 /2m = (2π/λ)2 /2m,

p p
2. In the relativistic case ω = E = m2 + p2 = m2 + (2π/λ)2 and E = m + K.
2π 1 λC
λ = p ≡p
m (E/m) − 1
2 (E/m)2 − 1
(
2π/E for ultrarelativistic case E >> m
→ √ (1.13)
2π/mv = 2π/ 2mK for the nonrelativistic case p << m
(a) where λC = 2π/m is the Compton’s wavelength for a particle of mass m.

(b) In the nonrelativistic case, where p << m and E '= m + K ' m + p2 /2m = m + mv 2 /2.
(c) For a nonrelativistic
√ molecule at temperature T , E = m + 3kB T /2, then K = 3kB T /2 and
λ = 2π/ 3mkB T .
(d) For the case T, v → 0 λ → ∞!, and QM effects are observable like in the case of the
Bose-Einstein codensate (BEC) [BEC]
3. The density of probability is ρ = |A|2 , the particle can be anywhere, with the same probability.
4. The flux of probability is constant too: J = (k/m)|A|2 = ρ v, where v = k/m is the classical
speed of the particle.
5. Notice the phase velocity is vp = ω/k = v/2, that is different from the classical one,
6. but the group velocity vg = ∂ω/∂k = v corresponds to the classical one.
7. The expectation values of the main operators are
R∞
−∞ dxψ (x)[−i∂/∂x]ψ(x)
∗
 = R∞ =k
−∞ dx|ψ(x)|
2
R∞
−∞ dxψ (x)Hψ(x)
∗
k2
<E> = R∞ = (1.14)
−∞ dx|ψ(x)|
2 2m
and < x >= 0.
8. ∆x = ∞, ∆p = 0 and by he Heisenberg principle ∆x∆p ≥ 1
9. The wavefunction has to be normalized to a Dirac Delta:
Z ∞
dxψk∗ (x)ψk0 (x) = δ(k − k 0 ) (1.15)
−∞
√
and ψk (x) = eikx / 2π
10. Up to an overall phase, without physical meaning (Gauge invariance) that we take equal zero.
11. Sometimes is convenient use the so called momentum space, obtained by simply taken the Fourier
transform of the wavefunction (equivalently, decomposing the wavefunction in plane waves):
Z Z
−ip·x d3 p ip·x
ψ(p) ≡ d xe
3
ψ(x), ψ(x) ≡ e ψ(p) (1.16)
(2π)3
12. For a plane wave one has that ψk (k 0 ) = δ(k − k 0 ).
13. It can be shown that is equivalent to take expectation values in both spaces: configuration or
momenta (see exercises).
14. A very interesting case is obtain

√ when the kinetic energy goes to zero and the wavefunction
becomes very large: λ = 2π/ 2mK. This the Bose-Einstein condensate (BEC).
15. The BEC was created by the first time by E. Cornell, W. Ketterle and C. Wieman (Nobel prize
2001) [BEC]. In that case the critical temperature to have it is Tc = (n/ζ(3/2)2/3 (4π 2 /mkB ),
where n is the particles density. T = 50 noK, n = 1.8 · 1014 cm3 for atomic hydrogen.
History and Phenomenology of de Broglie waves

Historically [7]
1. Electrons
(a) the first observation of the wave character of matter was done by Davisson(he share the
Nobel prize with G. Thomson in 1937) and Germer in 1927. They observed electrons with
energies of 30-600 eV scattered by Ni crystals (formed by accident!). A maximum was
found at an deviation angle of around 54o . No explanation can be given at least electrons
are assumed to behave like the matter waves proposed by de Broglie. Theoretically one
can understand the phenomena in the same way X-rays are scattered by crystals (Laue and
Bragg), even the same formula 2d sin φ = nλ (φ = π/2 − θ) is still correct. The electrons
wave length can be obtained from eV = ~ω = 2π~c/λ to get the λ = 1 Å for d = 1 Å. See
Figs. 1.4 for the diffraction pattern.
(b) Later a similar experiment was repeated by G. Thomson in 1927with electrons of higher
energies (10-40 keV) scattered by a crystals in powder(like for X-rays scattering of Debye-
Hull-Scherrer) observing as a diffraction patterns rings (see fig. 3-4 in Eisberg and Fig.
1.4). The bright zones are obtained at α = 2θBragg = tan−1 (R/L), dR/L = nλ, with R is
the radius of the ring, L the distance between the screen and the crystal powder and d the
interplanar distance in the crystal.
(c) The wave character of electrons have been employed in many areas like the Transmission
electron microscope (TEM), constructed by the first time in 1931 by E. Ruska (Nobel 1986)
and M. Koll.
(d) Besides other properties have been tested experimentally [7] like the cases of the two slits
Young experiment done by C. Jönson in 1961(d = 0.5 µm, E = 50 keV and λ = 0.05 Å)
with one (one electron interfering with itself) and with a beam of electrons, etc. See Fig.
1.4.
Figure 1.4: Electron diffraction: a) by a crystal (Davisson-Germer 1927) b) by crystals in powder (G.
Thomson 1927)
2. Similarly, beside the classical EM experiments with many photons the wave character of photon
has been tested with few and one photon again in agreement the expected. One has ‘one photon
interfering with itself’.
3. Neutrons
(a) Neutron waves [7] use was started by Fermi, Marshall and Zinn in 1946 .
(b) it was developed (in the 50-s) as a new Engineering tool in the 50-s by Brockhouse and
Shull (Nobel 1994).
(c) Beautiful experiments with neutrons have been done, in agreement with their wave char-
acter. These are the case of diffraction by a single slit, the Young two slits, and more slits
. See Fig. 1.5.
4. Additionally matter waves have been observed for α particles, atoms (He, with energies of 0.03
eV) and molecules by the first time by Esterman and Stern that observed the diffraction of a
Na beam by a NaCl surface.
5. Now they are used heavily in atomic beams interferometry where very high accuracy have been
reached, like measuring the gravity with an experimental error of 10−9 [9].
6. Finally experiments [7] have been done with large molecules like carbon-60, carbon-70 and
biomolecules like tetraphenylporphyrin.
Figure 1.5: Two-slit electron interference and diffraction: One by one n=1, 10, 1000 electrons, Jönson
1961 [7]. Electron and positron as particles of defined trajectories. Neutrons diffraction single slit,
Zeilinger. Neutron interference pattern for a double slit. Zeilinger.
Wavepackets
1. A particular case is the superposition of plane waves, like for example a Gaussian Packet
(Townsend p. 164):
q
1 2 2 √ 2 2
ψ(x, t = 0) = p√ e−x /2a +ik0 x ψ(k, t = 0) = 2 π a e−a (k−k0 ) /2 (1.17)
πa
in the coordinate and momentum spaces.
√
2. One can see that
√ < x >= 0, = k0 , < x2 >= a2 /2 and < p2 >= k 2 + 1/2a2 , so ∆x = a/ 2
0
and ∆p = 1/ 2 a.
3. The uncertainty principle is satisfied: ∆x∆p = 1/2.
4. Its time evolution can be obtained if one remember that each momenta component has a well de-
fined energy (E = p2 /2m) and its time evolution is governed by the time dependent Schrödinger
Equation (1.5).
5. The complete wavefunction is given by its superposition:

τ=0
0,5
τ=0.5
τ=1
0,4
τ=1.5
0,3
τ=2
2
|ψ|
τ=2.5
0,2
0,1
0,0
0 5 10 15 20 25 30
Figure 1.6: Time evolution of a wavepacket.
Z p √ Z 2 2
dk −i(Ek t−kx) 2 πa a k t
ψ(x, t) = ψ(k)e = dk exp − (k − k0 ) − i
2
− kx
2π 2π 2 2m
2
1 1 x k0 t
= p√ exp − − ik0 x −
π a(1 + it/ma2 ) 1 + it/ma2 2a2 2m

1 1 (ξ − 2ic) 2
= p√ exp − − 2c2
π a(1 + iτ ) 2 1 + iτ
1
|ψ(x)|2 = p exp −η 2 (1.18)
a π(1 + τ )2
√
with ξ = x/a, η = (ξ − 2cτ )/ 1 + τ 2 , τ = t/T , T = ma2 and c = k0 a/2 = k0 T /2ma = vT /2a.
p
6. One can obtain that < x >= 2acτ = vt, < x2 >= [1 + (1 + 8c2 )τ 2 ]a2 /2 and ∆x = a (1 + τ 2 )/2.
7. Similarly = 2c/a = k0 , < p2 >= [1 + 8c2 ]/2a2 , so < E >= [1 + 8c2 ]/4ma2 .
√ √
8. Finally ∆p = 1/a 2 and ∆x∆p = (1/2) 1 + τ 2 .
1.3.2 Step Potential

E > V0 case
√
In this case let us consider a wave of amplitude A and energy E (k = 2mE) coming p from the left.
Once it hit the step part of it reflects and the rest can be transmitted. Taking k 0 = 2m(E − V0 ) the
solution is
Figure 1.7: : Transmission and reflection coefficients for the rectangular potential step
0 0
ψI = Aeikx + Be−ikx , ψII = Ceik x + De−ik x (1.19)
The boundary conditions for a particle (wave) coming from the right that D = 0, and from the
continuity of the wavefunction and its derivative
A + B = C, k(A − B) = k 0 C (1.20)
that can be solved to obtain
k − k0
B/A = C/A = 2k/(k + k 0 ) (1.21)
k + k0
Given that the flux of probability is JI = (|A|2 − |B|2 )(k/m) and JII = |C|2 (k 0 /m) one can define
the ‘Reflection’ and ‘Transmission’ coefficients as
2 √ √ 2 p
k − k0 x− x−1 4kk 0 4 x(x − 1)
R = |B/A| =2
= √ √ , T = = √ √ 2 (1.22)
k + k0 x+ x−1 (k + k 0 )2 x+ x−1
with x = E/V0 and R + T = 1: One of two possibilities has to happens, the particle is reflected or
cross the step. In Optics, for normal incidence R = (1 − n)2 /(1 + n)2 , where n is the refraction index.
E < V0 case
The solution in this case is
ψI = Aeikx + Be−ikx , ψII = Ce−αx (1.23)

√ p
The boundary conditions are (k = 2mE and α = 2m(V0 − E)), now
A + B = C, ik(A − B) = −αC (1.24)

that can be solved to obtain
k − iα
B/A = C/A = 2k/(k + iα) (1.25)
k + iα
Given that the flux of probability is JI = (|A|2 − |B|2 )(k/m) and JII = 0. In this way R = 1 and
T = 0, the wave is totally reflected.
1.3.3 Potential Barrier (Ramsauer and Tunnel effects)

In this case the potential is V0 inside the region 0 < x < a and vanish outside.
E > V0 case(Ramsauer Effect)

The solutions to the Schrödinger Equation are, in the three regions
0 0
ψI = Aeikx + Be−ikx , ψII = Ceik x + De−ik x , ψIII = Eeikx (1.26)
√ p
with k = 2mE and k 0 = 2m(E − V0 ). Given that the potential is finite the wavefunction and
its derivative have to be continuous everywhere, in particular at x = 0 and x = a, so
A + B = C + D, k(A − B) = k 0 (C − D)
0 0
0 0

Ceik a + De−ik a = Eeika , k 0 Ceik a − De−ik a = kEeika (1.27)
Given that we are interested in the reflected and transmitted waves one should eliminate the
amplitudes C and D to obtain two remaining equations whose solution is
B (1 − n2 ) sin(k 0 a)
=
A (1 + n2 ) sin(k 0 a) + 2in cos(k 0 a)
E 2in exp(−ika)
= (1.28)
A (1 + n2 ) sin(k 0 a) + 2in cos(k 0 a)
with n = k 0 /k = λ/λ0 , the equivalent of the refraction index in Optics. In this way the reflection
and transmission coefficients can be obtained:
2
B (1 − n2 )2 sin2 (k 0 a)
R = =
A (1 + n2 )2 sin2 (k 0 a) + 4n2 cos2 (k 0 a)
2
E 4n2
T = =
A (1 + n2 )2 sin (k 0 a) + 4n2 cos2 (k 0 a)
2
√ −1
sin2 (c x − 1)
= 1+ (1.29)
4x(x − 1)
√
with x = E/V0 ≥ 1, c = 2mV0 a2 and again R + T = 1.
Figure 1.8: Transmission and reflection coefficients for the rectangular potential barrier. Ramsauer
and Tunnel effect . Negative resistance in he tunnel diode.
√
1. From the graph one can see that for c x − 1 = lπ (equivalently λ0 = 2a/l: the amplitude at the
interfaces is a maximum!) the transmission coefficient is one. One observe, too that the greater
the value of c more and narrower resonances are obtained.
2. This effect (Ramsauer effect) was discovered by Ramsauer and Townsend (1920) (Eisberg 218
and Gassiorowicz 79). It is obtained when a given gas is hited by a beam of electrons of energy
around 0.1 eV. The gas at this energy becomes transparent!.
3. An equivalent effect is obtained in Optics where a glass is recovered with a think film in order
to avoid unwanted reflections. In this case the condition for total transmission is k 0 a = lπ, so
again λ0 = 2a/l. The transmission coefficient is T = [1 + (1/4)(1/n − n)2 sin2 (2πa/λ0 )]−1 (Zhan
p.517).
E < V0 case, Tunnelling
Now the solution can be written as
ψI = Aeikx + Be−ikx ψII = Ce−αx + De+αx ψIII = Eeikx (1.30)

√ p
with k = 2mE and k 0 = iα = i 2mV0 (1 − x) (x < 1). The new solution can be obtained just
by replacing k 0 by iα to obtain in this case
2
B (1 + n2i )2 sinh2 (αa)
R = =
A (1 − n2i )2 sinh2 (αa) + 4n2i cosh2 (αa)
2
E 4n2i
T = =
A (1 − n2i )2 sinh2 (αa) + 4n2i cosh2 (αa)
√ −1 Z a
sinh2 (c 1 − x) p
= 1+ → exp −2 dx 2m [V (x) − E] (1.31)
4x(1 − x) 0
with ni = α/k.
1. The latest expression can be used for non rectangular barriers and it is going to be obtained
later on bay using the WKB method in chapter 5.
2. Tunnelling is observed in many systems like when wounded wires, become oxidize. In this case
electrons are still able to go from one to the other wire even if they do not have the needed
energy.
3. Another case is the α-decay where α particles are confined inside the nuclei and even if do not
have enough energy to scape the can because tunnelling. This was the first Strong Interacting
processed to admit a theoretical explanation, by Gamow, Condon and Guney in 1928 [15].
4. More examples are the NH3 molecule, the base for the first maser (later laser) constructed by
C. Townes in 1954 and winning the 1964 Nobel prize.
5. The Tunnel diode constructed by Leo Esaki in the lat 50-s (Nobel 1973). He won the Nobel prize
in 1973. In this case electrons tunnel through the badgap of a p-n junction and their modern
versions [Tunnel].
6. A final application is given by the Scanning tunnelling microscope (STM) constructed by the
first time by G. Binnig and H. Rohrer in 1981 (Nobel 1986) [Tunnel]. See photos obtained with
the STM in Fig. 1.9.
1.3.4 Infinite Potential Well

In this case one can take V (x) = 0 inside the well, 0 < x < a and infinite outside. The wavefunction
is ψ(x) = 0 outside the well, wile inside one has in general the two possible waves:
ψ(x) = Aeikx + Be−ikx (1.32)

√
with k = 2mE. Given that the wavefunction has to be continuous at both walls of the well one
has that ψ(0) = 0, so B = −A. In order to satisfy the boundary condition at wall in x = a k has to
be quantized: k = nπ/a with n is an integer. Normalizing the wavefunction the final result is
r nπx
2 n2 π 2
ψn (x) = sin En = (1.33)
a a 2ma2
Figure 1.9: Scanning tunnelling microscope (STM) picture of a stadium-shaped ”quantum corral”
made by positioning iron atoms on a copper surface. This structure was designed for studying what
happens when surface electron waves in a confined region. Courtesy, Don Eigler, IBM. Quantum
Mirage: A STM microscope was used to position 36 cobalt atoms in an elliptical quantum corral.
Electron waves moving in the copper substrate interact both with a magnetic cobalt atom carefully
positioned at one of the foci of the ellipse and apparently with a ”mirage” of another cobalt atom (that
isn’t really there) at the other focus. (Courtesy of IBM.) reported by: Manoharan et al., in Nature, 3
Feb. 2000 Electron Waves in a Plane: In this scanning tunneling microscope (STM) image, electron
density waves are seen to be breaking around two atom-sized defects on the surface of a copper crystal.
The resultant standing waves result from the interference of the electron waves scattering from the
defects. Courtesy, Don Eigler, IBM. ADN
1. Notice how the Sturm Theorem is obtained: the number of nodes of the wavefunction is equal
to n: zero for the ground state, one for the first exited one, and so on.
2. In the case the well in placed between −a/2 < x < a/2 the solution is (x → x − a/2))
r (
2 sin (nπx/a) for n = 2, 4, 6, · · ·
ψn (x) = (1.34)
a cos (nπx/a) for n = 1, 3, 5, · · ·
The energy spectra is the same.
3. In this case parity is well defined and its value is pn = (−1)n−1 .
4. Notice that E1 > 0, so due to the Heisenberg uncertainty condition the ground state energy can
not be zero!, as in the classical case. If it were the case =< p2 >= 0 and ∆p = 0 while
∆x ' a, violating the Heisenberg condition. Physical applications are in quantum dots and the
MIT bag model.
1.3.5 Finite Potential Well

In this case the potential vanish, except in the well (0 < x < a), where it is −V0 . See Merzbacher 105
and Gasiorowics 78 for the case −a/2 < x < a/2.
E>0
It is the same that in the case of the barrier (with E > 0), with V0 negative. The spectra is continuous
and scattering happens. One can obtain the solution for this particular case by taking V0 → −V0
(x → −x, c2 → −c2 , etc.). Thus from eq. (1.29) (Eisberg-Resnick 218)
2
B (1 − α2 )2 sin2 (k 0 a)
R = =
A (1 + α2 )2 sin2 (k 0 a) + 4α2 cos2 (k 0 a)
√ −1
sin2 (c x + 1)
T = 1+ (1.35)
4x(x + 1)
√ p
with k = 2mE, k 0 = 2m(E + V0 ) and α = k 0 /k. The physics obtained is the similar to the
barrier case, as it is shown in the plot above.
−V0 < E < 0

Here one obtain as solution, in the three regions
ψI = Aeαx , ψII = Beikx + Ce−ikx , ψIII = De−αx (1.36)

√ p
with α = −2mE and k = 2m(V0 + E). Boundary conditions imply
Figure 1.10: Finite width potential barrier. T as a function of x for c = 1, 10, and 50. Numerical
solution to eq. (1.40) for the same values of c.
A=B+C αA = ik(B − C)

Beika + Ce−ika = De−αa ik Beika − Ce−ika = −αDe−αa (1.37)
This a homogenous system of linear equations. There exists nontrivial solutions only if

1 −1 −1 0
1 −1 −1 0
α −ik ik 0 1 −iβ iβ 0
= =0 (1.38)
0 eika e−ika −e−αa 0 e ika e −ika −1

0 ikeika −ike −ika αe−αa 0 iβeika −iβe−ika 1
with β = k/α. The determinant can be computed to get
(1 − iβ)2 e−ika − (1 + iβ)2 eika = (1 − β 2 ) sin(ka) + 2β cos(ka) = 0 (1.39)
To obtain the equation, whose solutions determinate the energy levels
p
2β √ x(1 − x) √ p
tan(ka) = − , tan c 1 − x = − , sin[c 1 − x] = −2 x(1 − x) (1.40)
1−β 2 x − 1/2
p
with x = −E/|V0 | ∈ (0, 1) and c = 2m|V0 |a2 .
The number of possible states depends of the constant c: for large c one has many levels while if
c is small only few are allowed. If c << 1 one obtain that at least one solution there exist and can be
approximated as x ' c2 /4. This is shown in Fig 1.10.
c xn
1 0.19
(1.41)
10 0.3, 0.81
50 0.005, 0.022, 0.112, 0.178, 0.234, · · ·
Physical examples are the deuterium whose potential can be approximate by a finite well and has
only one level. More examples are the MIT ‘bag model’ for quarks inside the hadrons and a free
electron inside an ‘quantum wire’.
1.4 Harmonic oscillator (1-D)

In general all potential with a minima at x = a can be approximated by
1 1 1
V (x) ' V 00 (a)(x − a)2 = k(x − a)2 = mω 2 (x − a)2 (1.42)
2 2 2
The Schödinger Eq. can be written in this case
d2 ψ d2 ψ d2 ψ dψ
+ [2mE − m2 ω 2 x2 ]ψ = 0, + [λ − ξ 2 ]ψ = 0, 4z 2 + 2 + [λ − z]ψ = 0 (1.43)
dx 2 dξ 2 dz dz
with λ = 2E/ω = 2mE/α2 , α2 = mω, ξ = αx and z = ξ 2 . This is the ‘Weber equation’. In the
limit of ξ → ∞, ψ → A exp[−z/2], so one can try the solution of the form ψ = exp[−z/2]f (z) to get
for f

1 1−λ
zf 00 + − z f0 − f =0
2 4
f = AM (a, 1/2, z) + Bz 1/2 M (a + 1/2, 3/2, z)
∞
az a(a + 1) z 2 X (a)n z n
M (a, c, z) = 1 + + ≡ (1.44)
c 1! c(c + 1) 2! (c)n n!
n=0
with a = (1 − λ)/4 and M is the Confluent Hypergeometric function. The asymptotic behavior is
(Arken 757) for |z| → ∞ is:

Γ(c) z a−c (1 − a)(c − a)
M (a; c, z) → e z 1+ + ··· (1.45)
Γ(a) 1!z
Given that the asymptotic behavior of the wavefunction is
ψ = exp[−z/2]f (z) → exp[z/2]z a−1/2 (1.46)

1.4. HARMONIC OSCILLATOR (1-D) 33
0,8
0,7
0,7
0,6
0,6
0,5
0,5
0,4
0,4
ρ0
ρ1
0,3
0,3
0,2 0,2
0,1 0,1
0,0 0,0
-1,5 -1,0 -0,5 0,0 0,5 1,0 1,5 -2 -1 0 1 2
ξ 0,3 ξ
0,5
0,4
0,2
0,3
ρ10
ρ2
0,2 0,1
0,1
0,0 0,0
-3 -2 -1 0 1 2 3 -5 -4 -3 -2 -1 0 1 2 3 4 5
ξ ξ
Figure 1.11: Harmonic oscillator wavefunctions for several the ground and several exited states
This condition is unphysical so the boundary condition at infinity force us to end the series. This
is possible in two ways: First a = −l and B = 0 so
ψl (x) = Dl exp[−z/2]M (−l; 1/2, z), El = (2l + 1/2)ω (1.47)
The second possibility is a + 1/2 = −j and A = 0 for
ψj (x) = Ej exp[−z/2]z 1/2 M (−j; 3/2, z), Ej = [(2j + 1) + 1/2]ω (1.48)
In both cases the resulting polynomials are Hermite ones:
(2l)! 2(2j + 1)!

H2l (η) = (−1)l M (−l; 1/2, η 2 ), H2j+1 (η) = (−1)j ηM (−j; 3/2, η 2 ) (1.49)
l! j!
So both cases can be combined as:
r
α
ψn (x) = √ exp[−ξ 2 /2]Hn (ξ) ≡ Nn exp[−ξ 2 /2]Hn En = (n + 1/2)ω n = 0, 1, 2 . . . (1.50)
2n n!π
The energy levels are equally spaced. It should be noticed that the ground state does not correspond
to a zero energy, due to the Heisenberg principle (=< p2 >=< 2mE >= 0). This is the ‘zero
point’ energy. It is interesting to compare the quantum and classical density of probability.
The classical one is given by the time spend by the particle in an interval ∆x, 2∆t over the period:
∆Pclass = 2∆t/T (the factor two is because the particle cross the same interval twice in a given period).
Given than v = ∆x/∆t then ρclass = ∆Pclass /∆x = 2/vT . To express it as a function of the position
one can use the fact that
m 2 1 1
E= v + mω 2 x2 = mω 2 A2 = (n + 1/2)ω (1.51)
2 2 2
and x = A sin(ωt), so v 2 = (ωA)2 cos2 (ωt) = (ωA)2 (1 − x2 /A2 ). Thus the final expression is
1 α
ρclass. = √ = p (1.52)
2
π A −x 2 π 2(n + 1/2) − ξ 2
Practical applications are in Raman Spectroscopy, where it corresponds to the vibrational part of
the molecular spectra, as it will be seen later.
1.5. EXERCISES, SCHRÖDINGER EQUATION (1-D) 35
1.5 Exercises, Schrödinger Equation (1-D)
1.5.1 Matter waves
1. Compute λdeBroglie and ν for:

A: E 2 = m2 + p2 = m2 + k 2 = m2 + (2π/λ)2 then
2π 1 λC
λ = p ≡p
m (E/m)2 − 1 (E/m)2 − 1
(
2π/E for ultrarelativistic case E >> m
→ √ (1.53)
2π/mv = 2π/ 2mK for the nonrelativistic case p << m
where λC = 2π/m is the Compton’s wavelength for a particle of mass m. In the nonrelativistic
case, where p << m and E '= m + K ' m + p2 /2m = m + mv 2 /2. For √ a nonrelativistic
molecule at temperature T , E = m + 3kB T /2, then K = 3kB T /2 and λ = 2π/ 3mkB T .
case m λC λ 1/∆p ∼ 1/p

e− , K = 10 eV (Chemistry) 0.5 MeV 2480 f 3.9 Å 197.3 Å
e− , K = 50 eV (Davison-Germer) 0.5 MeV 2480 f 1.8 Å 39.5 Å
e− , E = 100 GeV (LEP II) 0.5 MeV 2480 f 0.012 f 0.002 f
γ, E = 10 eV (Chemistry) 0 ∞ 1240 Å 197. Å
γ, E = 10 MeV 0 ∞ 120 f 19.7 f
p, E = 1 TeV (Tevatron-Fermilab) 938 MeV 1.3 fm 1.2 · 10−3 f 2 · 10−4 f
p, E = 20 TeV (LHC) 938 MeV 1.3 fm 6.2 · 10−5 f 1 · 10−5 f
p, E = 1020 eV (Cosmic rays) 938 MeV 1.3 fm 1.2 · 10−11 f 2 · 10−12 f
4 He, K = 10 MeV (Rutherford) 4 uma 4.5 f 124 f
238 U 238 uma 0.0054 fm
T =v=0 m 6= 0 ∞
N2 , T = 300 o K 28 uma 0.27 Å
4 He, T =o K 4 uma 7.3 Å
BEC H, T = 10−9 o K 1 uma 0.08 mm
cell (µm) 0.3 ngr 6.2 · 10−30 m
virus (10 − 300 nm) −0 m
car, 2 T, v = 60 km/h 2T 10−45 m 1.9 · 10−38 m 3 · 10−39 m
Table: Values for several interesting de Broglie wavelenths.
2. Show that < pn > can be obtained equally in the space or momenta space
Z Z Z
d3 p d3 p n −ip·(x−x0 )
 =
n
ψ(p)∗ pn ψ(p) =
d xd x ψ(x ) ψ(x)
3 3 0 0 ∗
p e
(2π)3 (2π)3
Z Z
d3 p −ip·(x−x0 )
= d3 xd3 x0 ψ(x)∗ ψ(x)[i∇x ]n e
(2π)3
Z Z
3 0 0 ∗ d3 p −ip·(x−x0 )
= d xd x ψ(x ) [(−i∇) ψ(x)]
3 n
e
(2π)3
Z
= d3 xψ(x)∗ [−i∇]n ψ(x) (1.54)
where integration by parts was done and the Dirac’s delta representation was used. Notice that
consistency with the operator p = −i∇ interpretation is obtained.
3. Obtain, for the gaussian wavepacket x, x2 , ∆x and the corresponding quantities for p, etc. Hint:
1/2
∆O = < O2 > − < O >2
A:
Z Z
a a2
<x> = p dξ ξ exp[−η ], < x >= p
2 2
dξ ξ 2 exp[−η 2 ]
π(1 + τ 2 ) π(1 + τ 2 )

∂ψ ξ − 2ic ∂2ψ 1 (ξ − 2ic)2
= − ψ, =− − ψ
∂ξ 1 + iτ ∂ξ 2 1 + iτ (1 + iτ )2
Z Z
1 ∂2ψ 1
 = − 2
2
= 2 1 + iτ + 4c + 4ica dξξ|ψ| − a dξξ |ψ|
2 2 2 2
a ∂ξ 2 a (1 + iτ )2

1 2cτ 1 + 8c2 1 + 8c2
= 1 + iτ + 4c2
+ 4ica − a = (1.55)
a2 (1 + iτ )2 a 2a2 2a2
4. Draw the time evolution of density of probability for the gaussian wavepacket.
5. Workout the uncertainty principle for the gaussian wavepacket in the cases where a → 0, ∞
A: In the first case the position of the particle become well determinates, a (∆x → 0) but it
momenta is completely unknown: ∆p = ∞:
1
|ψ(x)|2 → δ(x − vt), lim exp[−x2 /a2 ] = δ(x) (1.56)
a→0 a
6. Estimate the time needed to spread out a macroscopic and a microscopic wavepacket, like the
gaussian case (see Townsend p. 164).
A: The time needed to have a significant spread out of the gaussian wave packet is T = ma2 =
ma2 /~c2 . For a microscopic object like an electron confined in a distance of the order of the
atom T = 0.5MeV · (10−10 m)2 /197.3MeV · 10−15 m · 3 · 108 m/s ∼ 10−18 sec. For a macroscopic
body T = ma2 = ma2 /~ ∼ 10−3 kg · (10−3 m)2 /10−34 J · s ∼ 1025 s ∼ 1017 years!.
7. For the free particle case write out the wavefunction for a given time as a function of the initial
one
A:
Z Z
dk dk
ψ(x, t) = ψ(k) exp[−i(Ek t − kx)] = dy exp[−iky]ψ(y, 0) exp[−i(Ek t − kx)]
2π 2π
Z r Z ∞
dk m im
= dy exp[−ik t/2m + ik(x − y)]ψ(y, 0) =
2
dy exp (x − y) ψ(y,
2
(1.57)
0)
2π 2πit −∞ 2t
8. Repeat what was done in the case of the Gaussian for the square wavepackets.
A: In this case [Gradshteyn 3.953, 3.462, 9.253, Abramowitz 297]
r Z a Z √m/2t x
m im A
ψ(x, t) = dy exp (x − y)2 A = √ √ dz cos z 2 + i sin z 2
2πit 0 2t iπ m/2t (x−a)
A h p p p p i
= √ C( mπ/4t x) + iS( mπ/4t x) − C( mπ/4t (x − a)) − iS( mπ/4t (x − (1.58)
a))
2i
where C(x) and S(x) are the Fresnel integrals.

9. Obtain the group and phase velocity for a relativistic particle. Is there any dispersion in the
wavepacket?.
p
A: R: Given that E = ω and p =pk, vf = ω/k = E/p = m2 + p2 /p = mγ/mγvc = 1/vc .
√
vg = dω/dk = d m2 + k 2 /dk = p/ m2 + p2 = vc and vf vg = 1
10. Workout the quarkonia (two quarks of mass m interacting with a potential V = F r) spectra by
using the Bohr model.
11. A neutron interferometer is constructed as shown in the Fig. Neutrons travel from A to D,
through the paths ABD and ACD to form an interference pattern in D. If the interferometer
is tilded by an angle δ around the axis AC, find the phase difference of the two rays (Sakurai
MQM version of Colella, Overhauser and Werner experiment [9]).
A:
p
ku
∆φ = (ku − kd )L2 = kd − 1 L2 = kd (pu /pd − 1)L2 = kd L2 [2m(E − mgL1 sin δ)]/2mE − 1
kd
p mgL1 L2 λ sin δ
= kd L2 1 − mgL1 sin δ/E − 1 ' −kd L2 (mgL1 sin δ/2E) = − (1.59)
2π~2
12. Obtain the corresponding Schrödinger integral equation [Landau-Paez, chap. 16 in ref [5]]
A: Taking the fourier transform of the SE one obtains the ISE in momenta space:
Z
q2 dk
ψ(q) + V (q − k)ψ(k) = Eψ(q) (1.60)
2m 2π
Figure 1.12: Figures corresponding to the 1D exercises. Colella experiment. semi-infinite well. Sym-
metric finite well. Odd and even wave function. Two semi-harmonic oscillator well. Dirac’s comb.
1.5.2 Other wells and steps
13. Do the problem of the Potential step again, but in the case the wave travels from left to right.
14. Workout the Gaussian wavepacket case colliding with a rectangular step (Schiff 105, A. Goldberg,
H. Schey and J. Schwartz, Am. J. Phys. 35, 177 (1977)).
15. Semi-finite well (1D), with potential (see Fig. 13)


 ∞ if x < 0
V (x) = −V0 if 0 < x < a (1.61)

0 if a < x
A: The solution can be written, for the Bounded states (V0 < E < 0)
0 0
ψI = Ae−ik x + Beik x , ψII = Ce−αx (1.62)
p √
with k 0 = 2m(E + V0 ) and α = −2mE. The boundary conditions are ψ(0) = 0, ψ(a− ) =
ψ(a+ ) and ψ 0 (a− ) = ψ 0 (a+ ) so B = −A and
2iA sin(k 0 a) = Ce−αa , 2ik 0 A cos(k 0 a) = −Cαe−αa (1.63)
thus the energy levels are obtained from the solutions of the equation tan(k 0 a) = −k 0 /α or
√ √ √
−x tan(c 1 + x) = − 1 + x (1.64)
with c2 = 2mV0 a2 and x = E/V0 . Notice that x = −1 is always a solution, independently of the
value of c. However it corresponds to no particle at all (A = B = C = k 0 = 0). Thus no physical
(with a particle inside) exists if c is too small). The solutions for several values of c are given in
the following table
c=0.1 no solution
c=1.6 0 Table: Roots of the eqs. (1.64).
c=10 -0.92, -0.68, -0.29
The solution for the continuous part (E > 0) of the spectra can be written as
ψI = A sin(k 0 x), ψII = Ceikx + De−ikx (1.65)

√
where now k = 2mE and given that ψ(0) = 0. The other boundary conditions, at x = a are
h i
A sin(k 0 a) = Ceika + De−ika , k 0 A cos(k 0 a) = ik Ceika − De−ika (1.66)
and solving for the reflected wave
(ik/k 0 ) tan(k 0 a) − 1
D = Ce2ika (1.67)
(ik/k 0 ) tan(k 0 a) + 1
and T = |D|2 /|C|2 = 1 as it should be.

16. For the potential of the form V (x) = (V0 /2m)δ(x) find out the reflection coefficient. Hint: Ob-
tain the boundary condition at x = 0.
√
A: The wavefunction is ( with k = 2mE)
(
Aeikx + Be−ikx for x < 0
ψ(x) = (1.68)
Ceikx for x > 0
The boundary conditions at x = 0 are ψ(0− ) = ψ(0+ ) and ψ 0 (0+ ) − ψ 0 (0− ) = V0 ψ(0), so
V0 A 2ikA
A + B = C, ik(A − B) = ikC + V0 C, B = − , C=
V0 + 2ik V0 + 2ik
|B|2 1 |C|2 4(k/V0 )2
R = = , T = = . (1.69)
|A|2 1 + 4(k/V0 )2 |A|2 1 + 4(k/V0 )2
As expected R + T = 1. If the potential is very strong (V0 → ∞) then R → 1 and T → 0, the
whole wave is reflected.
17. For the potential of the form V (x) = −(V0 /2m)δ(x) with V0 > 0 find the bounded states (E < 0).
Zettili 243 See Landau-Paez p. 233 in ref. [5]. Hint: Obtain the boundary condition at x = 0:
ψ 0 (0+ ) − ψ 0 (0− ) = −V0 ψ(0).
√
A: The Schrödinger eq., at x 6= 0 is ψ 00 (x) = α2 ψ(x) (α = −2mE) and the physical solution
for possible bounded states is

Ae−αx for x > 0
ψ(x) = (1.70)
Beαx for x < 0
Given that the wavefunction is continuous at the origin B = A and from the boundary con-
dition in the derivative one obtains
p that E = −V02 /8m is the unique bounded state and the
normalization constant is A = V0 /2.
18. Obtain the corresponding Schrödinger integral equation for the potential V (x) = −(V0 /2m)δ(x)
A: The fourier transform of the potential is V (k) = −V0 /2m and the ISE is:
Z
q2 V0 dk
ψ(q) − ψ(k) = Eψ(q) (1.71)
2m 2m 2π
19. For the potential of the form V (x) = −(V0 /2m) [δ(x − a/2) + δ(x + a/2)] with V0 > 0 find the
bounded states (E < 0). see Park 115 double wells, NH3, covalent bonds merzbacher 70. Do
the time dependent case to obtain oscillations between the two wells. Zettili 245.
√
A: The Schrödinger eq., at x 6= 0 is ψ 00 (x) = α2 ψ(x) (α = −2mE) and the physical solution
for possible bounded states is
ψI (x) = Aeαx , ψII (x) = Beαx ψI (x) + Ce−αx , ψIII (x) = De−αx (1.72)
The wavefunction is continuous at x = ±a/2 and its derivative satisfy the condition ψ 0 (±(a/2)+ )−
ψ 0 (±(a/2)− ) = −V0 ψ(±a/2) so
e−αa/2 A − e−αa/2 B − eαa/2 C = 0

−e−αa/2 A + e−αa/2 B − eαa/2 C = (V0 /α)e−αa/2 A
eαa/2 B + e−αa/2 C = e−αa/2 D
−eαa/2 B + e−αa/2 B = e−αa/2 D + (V0 /α)e−αa/2 D (1.73)
In order to have a novanishing solution one has to have

e−αa/2 −e−αa/2 eαa/2 0

−e−αa/2 [1 + V0 /α] e −αa/2 −e αa/2 0
=0
0 eαa/2 e −αa/2 −e −αa/2

0 eαa/2 e−αa/2 −(1 + V0 /α)e−αa/2
[1 + V0 /α]z 2 − (V0 /α)z + 1 = 0

p
V0 /α ± (V0 /α)2 − 4(1 + V0 /α)
z≡e =αa
(1.74)
4[1 + V0 /α]
20. Finite symmetric well (1D), with potential V (x) = V0 θ(|x| − a/2) (Schiff 40)

0 if |x| < a/2
V (x) = (1.75)
V0 if |x| > a/2
A: The solution can be written as, given the physical conditions at infinity
ψI = Aeαx , ψII = B cos(kx) + C sin(kx), ψIII = De−αx (1.76)
p √
with α = 2m(V0 − E) and k = 2mE and β = k/α. Besides at x = ±a/2,
Ae−αa/2 = B cos(ka/2) − C sin(ka/2), αAe−αa/2 = kB sin(ka/2) + kC cos(ka/2)

De−αa/2 = B cos(ka/2) + C sin(ka/2), −αDe−αa/2 = −Bk sin(ka/2) + Ck cos(ka/2)

e−αa/2 − cos(ka/2) sin(ka/2) 0

αe−αa/2 −k sin(ka/2) −k cos(ka/2) 0

0 cos(ka/2) sin(ka/2) −e−αa/2 =0 (1.77)

0 −k sin(ka/2) k cos(ka/2) αe−αa/2
where the last condition was obtained in order to have a novanishing solution. The determinant
can be written as

1 − cos(ka/2) sin(ka/2) 0
1 −β sin(ka/2) −β cos(ka/2) 0
= (sin(ka/2) + β cos(ka/2)) (cos(ka/2) − β sin(ka/2)) = 0
0 cos(ka/2) sin(ka/2) −1

0 −β sin(ka/2) β cos(ka/2) 1

(1 − β 2 ) sin(ka/2) cos(ka/2) + β cos2 (ka/2) − sin2 (ka/2) = 0
−2β
tan(ka) = (1.78)
1 − β2
On another side one can obtains
2B cos(ka/2) = (A + D)e−αa/2 , 2kB sin(ka/2) = α(A + D)e−αa/2

2C sin(ka/2) = (D − A)e−αa/2 , 2Ck cos(ka/2) = α(A − D)e−αa/2 (1.79)
There are two possibilities, the first C = 0, so D = A and the solution has positive parity:
ψ(x) = ψ(−x). The energy levels are determinated by the solutions of the equation
k tan(ka/2) = α, η = ξ tan ξ (1.80)
The second B = 0, so D = −A and the solution has negative parity: ψ(x) = −ψ(−x). The
energy levels are determinated by the solutions of the equation
k cot(ka/2) = −α, η = −ξ cot ξ (1.81)
with ξ = ka/2 and η = αa/2. In general is valid that
η 2 + ξ 2 = c2 /4 = 2mV0 a2 /4 (1.82)
Both equations agree with eq. (1.78). For small c there is always a solution, the even one. For
the case in witch c2 → ∞ the solutions are, as it should be
2n − 1
tan(ka/2) = ∞ and ka/2 = π,
2
− cot(ka/2) = ∞ and ka/2 = nπ, (1.83)
donde n = 1, 2, 3, . . ., or ka = nπ. The spectra is then En = (nπ/a)2 /2m.
21. Obtain the corresponding Schrödinger integral equation for the finite symmetric well (1D), with
potential V (x) = −V0 θ(|x| − a)
A: The fourier transform of the potential is V (k) = (2V0 /k) sin(ka/2) and the ISE is:
Z
q2 dk sin((q − k)a/2)
ψ(q) + 2V0 ψ(k) = Eψ(q) (1.84)
2m 2π q−k
1.5.3 Infinite well
22. Find, for an infinite potential well estimate the zero point energy, the lowest emited frecuency
and the temperature needed to emit it in physically interested cases
A:
case a E1 ν21 [hz] T [o K]

e− , atom, quantum dot 1 Å 38 eV 1.7 · 1017 1.8 · 106
e− , nucleus 1f 0.4 TeV 1.8 · 1027 1.8 · 1016
p 1 Å 0.02 eV 9 · 1013 928
p nucleus 1f 205 MeV 9 · 1023 9.5 · 1012
π, nucleus 1f 1.4 GeV 6.4 · 1024 6.5 · 1013
quark-u (mu ' 0.3 GeV), proton 1f 0.64 GeV 3 · 1024 3 · 1013
N2 , A = 28 1 mm 7 · 10−18 eV 0.03 3 · 10−13
cell (0.3 ngr) 20 µm 4 · 10−46 eV 1.8 · 10−30 1.9 · 10−41
Si (1 mgr) 0.5 mm 2 · 10−55 eV 9 · 10−40 9 · 10−51
ball, m = 20 gr 10 cm 2 · 10−64 eV 9 · 10−49 9 · 10−60
Table: Values for several interesting energies, emmited frecuencies and temperatures needed to
exited the first two levels. E1 = (π/a)2 /2m, ν21 = 3(π/a)2 /2m = 3E1 and T ' 2(π/a)2 /mkB =
4E1 /kB .
23. For an infinite potential well (0 ≤ x ≤ a) compute a) xnl , x2nl , ∆x, b) do the same in the classical
case, c) pnl , p2nl , ∆p and ∆x∆p, for a given state n d) do the same classically , e) write xnl and
pnl in matrix form and obtain [x, p], and f) Obtain v = pn /m, < K >, < V >, e) Obtain < E >
for an Boltzmann ensemble at temperature T
A: Using 2 sin a sin b = cos(a − b) − cos(a + b) one can reduces the integrals
Z nπx 1 Z a
2 a lπx (n − l)πx (n + l)πx
xnl = dx sin · x · sin = dx · x · cos − cos
a 0 a a a 0 a a
2 x=a
1 x a 2 (n − l)πx ax (n − l)πx
= δnl + cos + sin − (l → −l)
a 2 (n − l) π2 2 a (n − l)π a x=0

a a (−1)n−l − 1 (−1)n+l − 1
= δnl + 2 −
2 π (n − l)2 (n + l)2
Z a
2 nπx lπx
x2nl = dx sin · x · sin
2
a 0 a a
3 x=a
1 x 2a x
2 (n − l)πx ax2 2a3 (n − l)πx
= δnl + cos + − sin − (l → −l)
a 3 (n − l)2 π 2 a (n − l)π (n − l)3 π 3 a x=0

a2 2a2 (−1)n−l (−1)n+l
= δnl + 2 · (1 − δnl ) − (1.85)
3 π (n − l)2 (n + l)2
p
so (∆x)n = a 1/12 − 1/2π 2 n2 . Similarly
Z
2 a nπx −id
lπx

2ilπ a
Z nπx
lπx

pnl = dx sin · · sin =− 2 dx sin cos
a 0 a dx a a 0 a a

il (−1) n−l − 1 (−1) n+l −1
= +
a (n − l) 2 (n + l)2
2
Z a nπx −id 2
lπx

p2nl = dx sin · · sin
a 0 a dx a
Z a
2(lπ) 2 nπx lπx nπ 2
= − 3 dx sin sin = δnl (1.86)
a 0 a a a
p
so ∆p = nπ/a. The uncertainty principle is in this case ∆x∆p = nπ 1/12 − 1/2π 2 n2 . On
another side < E >=< K > + < V (x) >= (nπ/a)2 /2m (given that V (x) = 0).
24. For an infinite potential well Plot |ψ(x)|2 and |ψ(p)|2 , for n = 1 and n = 10.
25. A particle inside a perfect well of side a is in the ground state, suddenly the well expands to
have a side of 2a. What is the probability of finding the particle in the first excited state?
1.5.4 Harmonic Oscillator
26. Show that E > 0, using the Heisenberg uncertainty Principle (Zettili 252, Landau 83).
27. For an Harmonic Oscilator compute (see an alternative in chapter 3: the annihilation and
creation operators) a) xnl , x2nl , ∆x , b) pnl , p2nl , ∆p and ∆x∆p for a given state n, c) write xnl
and pnl in matrix form and obtain [x, p], d) Obtain v = pn /m, < K >, < V > and e) Obtain
< E > for an Boltzmann ensemble at temperature T
Z ∞ Z
−ξ 2 Nn Nm ∞ −ξ2
xnm = Nn Nm e Hn (ξ)xHm (ξ)dx = e Hn (ξ) [Hm+1 (ξ) + 2mHm−1 (ξ)] dξ
−∞ 2α2 −∞
Nn Nm √ 1 √ √
= [δn,m+1 + 2mδn,m−1 ] 2n π n! = √ n δn,m+1 + n + 1 δn,m−1 (1.87)
2α2 2α
1 h√ √ i iα h√ √ i
xn,l = √ l + 1δn,l+1 + lδn,l−1 pn,l = √ l + 1δn,l+1 − lδn,l−1
2α 2
1 hp p i
x2n,l = (l + 1)(l + 2)δn,l+2 + (2l + 1)δ n,l + l(l − 1)δn,l−2
2α2
α2 hp p i
p2n,l = − (l + 1)(l + 2)δn,l+2 − (2l + 1)δn,l + l(l − 1)δn,l−2 (1.88)
2
p p
and ∆x∆p = [< x2 > − < x >2 ] [< p2 > − 2 ] = < x2 >< p2 > = n + 1/2.
P −En /k T X
ne 1 1
B E ∂
n
<E> = P = − Z, β = , Z = e−βEn = βω/2
ne e − e−βω/2
−En /k B T ∂β kB T n
" 2 #
ω ω 1 ω
<E> = coth → kB T 1 − + ··· (1.89)
2 2kB T 2 kB T
when T → ∞, in agreement with the equipartition theorem. If T → 0 then < E >→ ω/2.
28. Obtain < V (x) > and < K(x) >, the average potential and kinetic energy for a given state in
the cases of a pure state |n > and for the general one.
A:
D m E m mω 2 1 1

< V >n = n ω 2 x2 n = ω 2 x2nn = · [(2n + 1)/2α2 ] = (n + 1/2)ω = En
22 2 2 2 2
p 1
< K >n = n n = p2nn /2m = α2 (2n + 1)/4m = (1/2)(n + 1/2)ω = En (1.90)
2m 2
so < V >n =< K >n = (n + 1/2)ω/2.
29. Obtain Hnl = p2nl /2m + (mω 2 /2)x2nl = (n + 1/2)ωδnl
30. For a Harmonic Oscillator Plot |ψ(x)|2 and |ψ(p)|2 , for n = 1 and n = 10.
31. Compute, for a Harmonic oscillator the probability to find the particle outside of the classical
allowed region, for n = 0 and for n = 10.
P
32. A given state of a Harmonic Oscillator is given by the wavefunction: ψ = 4i=1 ai ψi . Compute
the energy of this state.
33. An oscillator is in the state ψ = aψ0 + bψ1 . Find ∆x∆p.

A:

a∗ eiωt/2 < 0| + b∗ e3iωt/2 < 1| x ae−iωt/2 |0 > +be−3iωt/2 |1 >
<x> =
|a|2 + |b|2
√ √
2Re a∗ be−iωt 2 |a∗ b|
= = cos(ωt) (1.91)
α [|a|2 + |b|2 ] α [|a|2 + |b|2 ]
that oscillates at the classical frequency!.
34. Show that a wave packet in a Harmonic oscillator potential moves as a whole at a frequency
equal to the classical one (Schiff page?).
35. The molecule of C2 has a natural frequency of ν = 4.9 · 1013 Hz. a) Compute the equivalent
‘spring constant’, and compare it with a typical one for a lab. spring. b) the average size of the
vibrations < x >rms and c) What is the temperature need to be able to ‘see’ the vibration and
the rotation spectra (Raman Spectra). H2+ : ν̄0 = 2297 cm−1 ≡ 1/λ (1 cm−1 = 3 · 1010 hz). H2 :
ν̄0 = 4395 cm−1 . CO: ν̄0 = 2170 cm−1 (page 69, sec. 4.3.1 on Raman spectroscopy)
p
A:
p a) k = mω 2 = m(2πν)2 = 640 N/M, a macroscopic value!, b) x
rms = (1/α) n + 1/2 =
(n + 1/2)~λ/4πmc = 0.06 Å. kB T = ~ω = 2π~c/λ → and c) T = 2π~c/λkB = 2π · 10−34 · 3 ·
108 /1.23 · 10−23 ' 3325 o K.
36. Work out the harmonic oscillator in presence of an electric field, in general:
1
V = mω 2 x2 − eEx + V0 (1.92)
2
37. Work out the case of two coupled oscillators (Zettili 259)
1
V = µω 2 (x1 − x2 )2 (1.93)
2
1.5.5 Other Potentials
38. Solve the SE for the potential V = F x (like the gravitational or electric constant fields. For the
experimental side see ref. [9]).
A: The SE is

1 d2 d2
− + F x ψ = Eψ, − ξ ψ = 0, ψ = AΦ(ξ) (1.94)
2m dx2 dξ 2
where ξ = (2mF )1/3 (x − E/F ) and the regular solution at the origin is the Airy function
(see the appendix). There are three interesting solutions. The ‘free fall’ or continuous case
where the energy can have any value and the normalization constant can be obtained to be
|A|2 = (4m2 /π F )1/3 (Landau 88). A second possibility is obtained when the particle is not
allowed to be in region x < 0 (equally V (x < 0) = 0 and when. In these cases the spectra is
given
1/3
F2
En = xn (1.95)
2m
where xn are the roots of the Airy function, Φ(−xn ) = 0 (see Appendix). see Fig. 14.a. Finally
a third possibility is obtained when the potential is V (x) = F |x|, the solution is then
1/3
F2
En = zn (1.96)
2m
where zn = yn (the roots of the first derivative of the Airy function, Φ0 (−yn ) = 0 for an even
wavefunction and zn = xn when the wavefunction is odd (see Fig. 14.b). A semiclassical
treatment of this problem is given in ref. [17] and it provides a crude model for the interquark
potential abe to take into account quark confinement as well as the Quarkonium spectra.
39. Double oscillator, Merzbacher 65.
(
mω 2 (x + a)2 for x < 0
V (x) = (1.97)
2 (x − a)2 for x > 0
A: The SE becomes (α2 = mω, E = (ν + 1/2)ω, z = α2 (x ± a)2 for x < 0 and x > 0, respectively

d2
− α(x ± a)2
+ 2mE ψ=0
dx2
zψ 00 + (1/2 − z)ψ 0 + (ν/2)ψ = 0 (1.98)
with the solution, satisfying the boundary conditions at x → ±∞
ψ = AU (−ν/2, 1/2, z) exp[−z/2] (1.99)
with different constants for x positive and negative. The boundary conditions, taking into
account parity become ψ 0 (0) = 0 and ψ(0) for even and odd parities, respectively. This the
solution is
(
±1 for x < 0
ψ = A exp[−z/2]U (−ν/2, 1/2, z) × (1.100)
1 for x > 0
40. Do the problem of the double finite square well: a) obtain the reflection and transmission
coefficients and b) the energy values for the discrete spectra. Do the time dependant case to
obtain oscillations between the two wells.
41. Show the Bloch’s theorem (Sakurai 261)
42. Periodic Kronig-Penney potential. Show that for a periodic potential, with period a (V (x + a) =
V (x)) the solution can be written as ψ(x + na) = eiqx uq (x) with uq a periodic function of period
a, or ψ(x + na) = einqa ψ(x) (Floquet’s Theorem). Bransden 182, exer. 4.20 (a → ∞, bands
tend to a discrete spectrum) 192, Flügge 62.
A: The operator translation by a distance a, defined as Ta ψ(x) = ψ(x + a) commutes with the
Hamiltonian. Therefore it can be diagonalized simultaneously. Let ψ1,2 be two independent so-
lutions of the SE. Thus the general solution ψ = aψ1 +bψ2 , as well as ψ1,2 must be eigenfunctions
of Ta :
ψi (x + a) = Ci1 ψ1 (x) + Ci2 ψ2 (x) = λψi (x)

ψ(x + a) = d1 ψ1 (x) + d2 ψ2 (x) = a1 ψ1 (x + a) + a2 ψ2 (x + a)
= [a1 C11 + a2 C21 ]ψ1 (x) + [a1 C12 + a2 C22 ]ψ2 (x) = λψ(x) (1.101)
The last equality has a novanish solution only if

C11 − λ C21
=0
C12 C22 − λ
has two solution λ1,2 and the Wroskian of the two eigensolutions W (ψλ1 , ψλ2 ) is from one side
periodic and as it is well known (see pe Arfken [5]) is constant. Therefore
W (x + a) = λ1 λ2 W (x) = const. (1.102)
so λ1 λ2 = 1. Given that ψ(x + na) = λn ψ(x) = finite for all n, it follows that λ1 = eiqa and
λ2 = e−iqa . Thus one has that ψ(x + na) = eniqx ψ(x) that it is satisfy only if ψ(x) = eiqx uq (x)
with uq (x + a) = uq (x).
P
43. Find the spectra for the ‘Dirac’s comb’ potential: V (x) = (V0 /2m) n δ(x − na)
A: The solution in the cells 0 < x < a and a < x < 2a can be written in general as
(
Aeikx + Be−ikx for 0 < x < a
ψ(x) = (1.103)
Aeik(x−a) + Be−ik(x−a) for a < x < 2a
Boundary conditions at x = a imply that
Aeika + Be−ika = A + B, ik[Aeika − Be−ika ] = ik(A − B) + V0 (A + B) (1.104)

that can be solved to produce the equation
cos(ka) − 1 = V0 /2k sin(ka) (1.105)
whose solutions are bands of energy.

Chapter 2
Schrödinger Equation 3D
2.1 Center of mass motion

The Hamiltonian for the case of two particles, in general
p21 p2
H= + 2 + V (r1 , r2 ) (2.1)
2m1 2m2
Using the coordinates of the center of mass and relative motion: r = r2 − r1 and R = [m1 r1 +
m2 r2 ]/(m1 + m2 ) one has that
2
2m1 m1
41 = 4− ∇ · ∇R + 4R
m1 + m2 m1 + m2
2
2m2 m2
42 = 4+ ∇ · ∇R + 4R (2.2)
m1 + m2 m1 + m2
to obtain for the Schrödinger Eq.

1 1
− 4− 4R + V (r, R) ψ(r, R) = ET ψ(r, R) (2.3)
2µ 2M
with M = m1 +m2 and µ = m1 m2 /M . In the case the potential can be written as V (r, R) = V (r)+
Vext. (R) The solution can be written as ψ(r, R) = ψCM (R)ψ(r), to separate the two contributions
satisfying the equations

1 1
− 4R + Vext. (R) ψ(R) = ECM ψ(R), − 4 + V (r) ψ(r) = Eψ(r) (2.4)
2M 2µ
and ET = ECM + E. The CM motion in the due to the external sources of interaction, like in the
case of a insulated system
ψCM = AeipCM ·R (2.5)

with ECM = p2CM /2M . It remains to solve the internal part, as will be done analytically , for
several case in the following.
51
52 CHAPTER 2. SCHRÖDINGER EQUATION 3D
2.2 Cartesian coordinates

2.2.1 Plane waves, free particle (3-D)
For a free particle the wave equation is ∇2 ψ = 2mEψ, and its solution can be obtained easily, with
the normalization condition
Z
1 k2
ψ= eik·x
, E k = ; d3 xψk∗ (x)ψk0 (x) = δ (3) (k0 − k) (2.6)
(2π)3/2 2m
2.2.2 Particle in a perfect box

In this case the particle is inside a perfect box of sides a, b and c. It is the same as the free particle
except it has to satisfy the boundary conditions. The solution is, then (with n1, 2, 3 = 1, 2, 3, 4, · · · )
r n πx n πy n πz
8 1 2 3
ψn1 n2 n3 = sin sin sin ,
V a b c

1 n 1 π 2 n 2 π 2 n 3 π 2
En1 n2 n3 = + + (2.7)
2m a b c
2.2.3 Anisotropic Harmonic oscillator (3-D)

In general all potential with a minima at a = (a, b, c) can be approximated by (the mixed terms can
be eliminated by choosing appropriately the axis to diagonalize the quadratic form)

1 ∂2V ∂2V ∂2V
V (x) ' (x − a) +
2
(y − b) +
2
(z − c)2
2 ∂x2 ∂y 2 ∂z 2
1 2
= m ω1 (x − a)2 + ω22 (y − b)2 + ω32 (z − c)2 (2.8)
2
The Schödinger Eq. can be written in this case (x → x + a)

∇2 ψ + 2mE − m2 ω12 x2 + ω22 y 2 + ω32 z 2 ψ = 0
1 d2 ψ1 1 d2 ψ2 1 d2 ψ3
+ + + 2mE − α14 x2 − α24 y 2 − α14 z 2 = 0 (2.9)
ψ1 dx2 ψ2 dy 2 ψ3 dz 2
with ψ(r) = ψ1 (x)ψ2 (y)ψ3 (z),
d2 ψi
+ [λi − ξi2 ]ψi = 0 (2.10)
dξi2
with λi = 2Ei /ωi = 2mEi /αi2 , αi2 = mωi and ξi = αi xi (no sum), and similarly for the other
components. Naturally E = E1 + E2 + E3 . Thus the normalized solution is
2.3. CENTRAL POTENTIALS 53
r
αi
ψi (x) = √ exp[−ξi2 /2]Hni (ξi ), Ei = (ni + 1/2)ωi n1 = 0, 1, 2 . . .
2ni ni ! π
r
α1 α2 α3
ψ(x) = exp[−(ξ12 + ξ22 + ξ32 )/2]Hn (ξ1 )Hn (ξ2 )Hn (ξ3 )
2 1 2 3 n1 !n2 !n3 !π 3/2
n +n +n
≡ N exp[−(ξ12 + ξ22 + ξ32 )/2]Hn1 (ξ1 )Hn2 (ξ1 )Hn3 (ξ1 )

E = (n1 + 1/2)ω1 + (n2 + 1/2)ω2 + (n3 + 1/2)ω3 (2.11)
That in the isotropic case becomes E = (n1 + n2 + n3 + 3/2)ω.
2.2.4 Particle in a Magnetic Field

The Hamiltonian for a charged particle in a constant magnetic field, B (taken in the z-direction) is
(See Liboff 418. )
1 1
H= (p − eA)2 = (px + eyB)2 + p2y + p2z (2.12)
2m 2m
where the magnetic field is related to the vector potential as A = (−yB, 0, 0) when the z-axis is
chosen along the magnetic field. The solution can be obtained as ψ = A exp[i(kx x + kz z)] · f (y) and
1
Hψ = (kx + eyB)2 + p2y + kz2 ψ = Eψ,
2m " #
1 p2y 1 kz2
(kx + eyB) + py f (y) =
2 2
+ mΩ (y + y0 ) f (y) = E −
2 2
ψ (2.13)
2m 2m 2 2m
with Ω = eB/m the cyclotron frequency and y0 = kx /eB. The equation for f is the one for the
harmonic oscillator, so the final solution is
Nn i(kx x+kz z)−ξ2 /2

ψn,kx kz = e Hn (ξ), En,kx kz = (n + 1/2)Ω + kz2 /2m (2.14)
2π
with ξ = α(y + y0 ), Nn the normalization constant of the harmonic oscillator and α2 = mΩ. The
energy levels are referred as Landau Levels.
2.3 Central Potentials

In the case the potential is central (V (r) = V (r)) is better to use spherical coordinates to obtain

1 1 ∂ 2∂ 1 1 ∂ ∂ 1 ∂2
− r + sin θ + ψ(r) + V (r)ψ(r) = Eψ(r) (2.15)
2µ r2 ∂r ∂r r2 sin θ ∂θ ∂θ sin2 θ ∂φ2
Taking ψ(r) = R(r)Ylm (Ω) = R(r)Θ(θ)Φ(φ) one obtains (see orbital momenta section in the
Angular momenta chapter) that

1 00 2 0
− R + R + Veff. (r)R(r) = ER(r)
2µ r
l(l + 1)
Veff. (r) = V (r) + (2.16)
2µr2
that can be rewritten in terms of R = u/r as
1 00
− u + Veff. (r)u(r) = Eu(r) (2.17)
2µ
Given that R has to be finite at r → 0 on has that u(r → 0) → 0. The normalization conditions
are
Z ∞ Z ∞
drr |R(r)| =
2 2
dr|u(r)|2 = 1 (2.18)
0 0
It is easy to show that for central potentials such that
1. if V (r → 0) → 1/rs , with s < 2 the wavefunction behaves as R(r → 0) → rl . So Rnl (r → 0) =

Rns (0)δl0 .
2. Similarly, for central potentials the parity of an eigenstate of angular momenta l is (−1)l :
P |nlm >= (−1)l |nlm >.
2.3.1 Spherical Waves

For the case of a free particle or spherical waves the potential energy vanish. The radial part of the
Schrödinger eq. becomes
2 l(l + 1)
Rl00 + Rl0 − Rl = −2µERl (r)
r r2
d2 2 d l(l + 1)
Rl + Rl − Rl + Rl (r) = 0 (2.19)
dρ 2 ρ dρ ρ2
with ρ = kr and k 2 = 2µE. This is the Spherical Bessel Eq. with general solution Rl (r) =
Al jl (ρ) + Bl nl (ρ) (the Spherical Bessel and Neuman functions. Arfken 622). The boundary condition
at r = 0 implies that Bl = 0, so the solution is ψklm = Al jl (kr)Ylm (θ, φ). This wavefunction can be
normalized as
Z
∗
drr2 dΩψklm ψk0 l0 m0 = δ(k − k 0 )δll0 δmm0
Z ∞
1
dρρJν (αρ)Jν (α0 ρ) = δ(α − α0 ) (2.20)
0 α
p
where the last identity is valid for ν > −1/2 (Arfken 594) and it is used with jl (x) = π/2xJl+1/2 (x)
(Arfken 623) to obtain the normalized wavefunction
r r
2 2 1
ψklm = kjl (kr)Ylm (θ, φ) → sin(kr − lπ/2)Ylm (2.21)
π π r
Where the limit is taken when r is large. Notice that this is consistent with probability (or energy)
conservation for spherical waves.
2.3.2 Infinite spherical bag

In this case the particle can be inside a perfect bag of radius a, and the solution is the same as in
the former case: Rl (r) = Al jl (kr) (k 2 = 2µE), while vanish outside. The boundary condition at the
surface of the sphere implies that Rl (a) = Al jl (ka) = 0, so ka = xnl the roots of the l-th Spherical
Bessel function: jl (xnl ) = 0. Then the normalized solution is (see Appendix, spherical Bessel function)
a3 x2nl
ψnlm = Anl jl (xnl r/a)Ylm (θ, φ), |Anl |−2 = [jl+1 (xnl )]2 , Enl = (2.22)
2 2µa2
ln 1 2 3 4 5
s π 2π 3π 4π 5π
p 4.4934 7.7252 10.9041 14.0662 17.2208
d 5.7635 9.0950 12.3229 15.5146 18.6890
f 6.9879 10.4171 13.6980 16.9236 20.1218
g 8.1826 11.7049 15.0397 18.3013 21.5254
Table 1: Spherical Bessel roots. They can be approximate as xnl ∼ (n + l/2)π.
1. One physically application of this simple model is to Nuclear Physics where the potential acting
over a nucleon (proton or neutron) inside a given nuclei can be modelled as the ‘perfect bag’ (of
course it is a very rude oversimplification), as in the case of large nucleus and it is the base for
the Fermi gas model.
2. This simple model is able to explain the ‘magic’ numbers (Townsend 296 and Eisberg 575): the
nuclei with these number of protons and neutrons are more stables that the others.
3. These number can be understood in the Shell Model of Nuclear Physics: when a given shell is
full the corresponding nuclei is more stable
(a) In the periodic table where the numbers are 2 (He), 10 (Ne), 18 (Ar), 36 (Kr), 54 (Xe), 86
(Rn) electrons).
(b) The experimental ‘magic numbers’ are 2, 8, 20, 28,50, 82 and 126 [15].
(c) In the case of the perfect bag the numbers would be 2, 8, 18, 20, and so on.
These can be seen in the graph of the spectra bellow. The difference is, of course due to the lack
of these very simple potential to reproduce the real one, where for example the spin-orbit and
spin-spin, etc. interactions have to be included (Cottingham 24 and Townsend 296).
4. More applications are in hadronic physics where quarks are confined inside mesons and barions,
like in the MIT bag mode.
2g
611 3p
2µa2 Enl 2f
3s
9 2d
1g
2p
7 1f
2s
5 1d
1p
1s
Perfect bag
3
s, l = 0 p, l = 1 d, l = 2 f, l = 3 g, l = 4 h, l = 5
Figure 2.1: ‘Perfect’ spherical bag spectra 2µa2 Enl = x2nl , with n2S+1 LJ .
2.3.3 Finite spherical bag

The potential is in this case V = −V0 inside the bag (r < a) and vanish outside. In this section we
are going to solve for the discrete spectra: E < 0. The differential equations, inside and outside are,
respectively

2 0 l(l + 1)
Rl00 + Rl − ∓ 1 Rl = 0 (2.23)
ρ ρ2
for r < a and r > a, respectively. The derivatives are taken with respect to ρ = kr for r < a and
ρ = αr for r > a. Besides k 2 = 2µ(V0 + E) ≥ 0 and α2 = −2µE ≥ 0. The solution is, taken into
account the boundary conditions at the origin and at infinity
(
Al jl (kr) for r < a
Rl = (1) (2.24)
Bl hl (iαr) for r > a
(1, 2)
given that hl (iαr) → exp[±αr]. From continuity of the logarithmic derivative one has that
(1) 0
j 0 (ξ) h (iη)
ξ l = iη l(1) (2.25)
jl (ξ) h (iη)
l
with ξ = ka and η = αa (They are not independent but satisfy the relation ξ 2 +η 2 = c2 = 2µV0 a2 ).
This equation can be specialized to
ξ cot ξ = −η, l=0

(1 + η)ξ + η (1 − ξ cot ξ) = 0, l = 1
2 2
−9 + 4ξ 2 + (9 − ξ 2 )ξ cot ξ 9 + 9η + 4η 2 + η 3
= − , l=2 (2.26)
3 − ξ 2 − ξ cot ξ 3 + 3η + η 2
and so on.
p
1. Notice that in this case if c ≤ π/2 no a bound state are possible, contrary to the one dimen-
sional case. It corresponds to ξ = π/2, V0 = k 2 /2µ, and E = 0 the ‘mouth of the well’. The first
equation (for l = 0) is exactly the same for the 1D finite well, for even functions (R1s (0) 6= 0).
η > 0, otherwise particles can be at infinite. ±η produce the same solutions for the energy and
the wavefunction.
2. In the physical case of Deuterium there is only one bound state.
Once the solutions, ξnl of these equations are obtained the energy spectra can be computed as
2 /c2 )V .
Enl = (−1 + ξnl 0
c=2 ξ1s =1.895494

c=4 ξ1s =2.474577 ξ1p =3.471965
c=6 ξ1s =2.6788 ξ2s =5.22596 ξ1p =3.8115 ξ1d =4.8548
c=15 ξns =2.9440 5.8803 8.798 11.6744 14.4169
ξnp =4.20936 7.2236 10.1613 13.0186
ξnd =5.39698 8.4959 11.4595 14.2756
Table 2: Roots of the eqs. (2.26).
c=2 E1s /V0 =-0.102

c=4 E1s /V0 =-0.617 E1p /V0 =-0.2466
c=6 E1s /V0 =-0.801 E2s /V0 =-0.241 E1p /V0 =-0.596 E1d /V0 =-0.3453
c=15 Ens /V0 =-0.961 -0.846 -0.656 -0.394 -0.076
Enp /V0 =-0.921 -0.768 -0.5411 -0.2467
End /V0 =-0.8705 -0.679 -0.4164 -0.0943
Table 3: Energetic spectra (Enl /V0 ) for the spherical finite bag.
The wavefunction is then, with its normalization condition
(
jl (ξr/a) for r < a
Rl = Al h (1)
i
(1)
jl (ξ)/hl (iη) hl (iηr/a) for r > a
 
Z 1 j (ξ) 2 Z ξ
l (1)
|Al |2 a3  [jl (ξx)]2 x2 dx + (1) [h (iηx)]2 x2 dx = 1 (2.27)
0 h (iη) 1 l
l
6-0.1
5s 4d
2µa2 Enl
4p
-0.3
4s 3d
-0.5
3p
3s
2d
-0.7
2p
2s
1d Finite bag
-0.9 1p
1s
s, l = 0 p, l = 1 d, l = 2 f, l = 3 g, l = 4 h, l = 5
Figure 2.2: Finite spherical bag spectra Enl /V0 , with c = 15 and n2S+1 LJ .
2.3.4 Isotropic harmonic oscillator

In this case the radial equation

2 0 1 2 2 2 l(l + 1)
Rl00
+ Rl − µ ω r + − 2µE Rl = 0
r 2 r2
2
d 2 d l(l + 1)
+ 2
−ρ − + λ Rl (r) = 0 (2.28)
dρ2 ρ dρ ρ2
√
with ρ = µω r, α2 = µω and λ = 2E/ω. The solution can be written, using R = exp[−ρ2 /2] ρl W
as

00l+1
W +2 − ρ W 0 − (3 + 2l − λ)W = 0
ρ
2
d 2l + 3 d 1
z 2+ −z + (λ − 2l − 3) W (z) = 0 (2.29)
dz 2 dz 4
with z = ρ2 . The general solution is W = AF +BF/z l+1/2 with a = −(λ−2l−3)/4 and c = l+3/2.
Given that it has to be finite at the origin then B = 0 and

2 /2 2l + 3 − λ 2l + 3 2
Rnl = e−ρ ρl F , ,ρ (2.30)
4 2
Besides it has to vanish at infinity for a bounded state (all physical states have to be bounded in
this case). The asymptotic behavior is
611 3s 2d 1g
2Enl /ω
9 2p 1f
7 2s 1d
5 1p
3 1s Isotropic oscillator
s, l = 0 p, l = 1 d, l = 2 f, l = 3 g, l = 4 h, l = 5
Figure 2.3: Isotropic harmonic oscillator spectra Enl = (2n + l + 3/2)ω, with n2S+1 LJ .
2
−ρ2 /2 leρ
Rnl → e ρ 2 c−a → ∞ (2.31)
(ρ )
so one has that (2l + 3 − λ)/4 = −n = integer. Thus the solution is given as (it can be written in
terms of the associated Hermite polynomials too B.39, [5])

−ρ2 /2 l 2l + 3 2
ψnlm = Nnl e ρ F −n, , ρ Ylm , En,l,m = (2n + l + 3/2)ω
2
Γ(n + l + 3/2)
|Nnl |2 = 2(µω)3/2 (2.32)
Γ(n + 1)Γ2 (l + 3/2)
Examples are, for s-states
1/2
1/2
4 −ρ2 /2 6 −ρ2 /2 2 2
R00 = √ (µω)3/2 e , R10 = √ (µω) 3/2
e 1− ρ
π π 3
1/2
15 2 4 4
R20 = √ (µω)3/2 e−ρ /2 1 − ρ2 + ρ4
2 π 3 15
1/2
35 −ρ2 /2 4 4 8 6
R30 = √ (µω) 3/2
e 1 − 2ρ + ρ −
2
ρ (2.33)
4 π 3 15 · 7
for p-states
1/2 1/2
8 20
−ρ2 /2 −ρ2 /2 2 2
R01 = √ (µω)3/2 e ρ, R11 = √ (µω)3/2 e 1− ρ ρ
3 π 3 π 5
1/2
35 −ρ2 /2 4 2 4 4
R21 = √ (µω)3/2
e 1− ρ + ρ ρ (2.34)
3 π 5 35
and for d-ones
1/2 1/2
16 −ρ2 /2 2 7·8 −ρ2 /2 2 2 2
R02 = √ (µω) 3/2
e ρ , R12 = √ (µω)3/2
e 1− ρ ρ
15 π 15 π 7
1/2
42 2 4 4 4
R22 = √ (µω)3/2 e−ρ /2 ρ2 1 − ρ2 + ρ (2.35)
5 π 7 7·9
2.3.5 Coulomb potential, Hydrogenic atoms

The interest in Hydrogenic atoms is very wide [Hadronic atoms, Rydberg atoms]. In general the atom
is bounded by the Coulombic potential V = −Ze2 /4π0 r = −Zα/r. So one has to solve the radial
equation:

2 0 2µZα l(l + 1)
Rl00
+ Rl + − + 2µE Rl = 0
r r r2
2
d 2 d λ l(l + 1) 1
+ + − − Rl (r) = 0 (2.36)
dρ2 ρ dρ ρ ρ2 4
where λ = 2µZα/β, β 2 = −8µE > 0 (for bounded states) and ρ = βr. By transforming Rl =
exp[−ρ/2]ρl F (ρ) the equation becomes
ρF 00 + [2(l + 1) − ρ] F 0 + (λ − l − 1)F = 0 (2.37)
again the Hypergeometric Confluent equation with a = l + 1 − λ and c = 2(l + 1). The solution
has to be finite at the origin, so one has that F = AF (l + 1 − λ, 2(l + 1), ρ). Given that we are looking
for atoms (bounded systems) the wavefunction has to be finite at infinity so a = l + 1 − λ = −n̄,
with n̄ = 0, 1, 2, · · · . Then n ≡ λ = n̄ + l + 1 = 1, 2, 3 · · · and the Energy becomes quantized:
En = −(µ/2)[Zα/n]2 . Notice that n̄ = n − (l + 1) ≥ 0 and 0 ≤ l < n. The radial solution can be
written in terms of the Associated Laguerre Polynomials (Arfken 755):
Rl = Ae−ρ/2 ρl F (l + 1 − n, 2(l + 1), ρ)

n̄!m!
F (−n̄, m + 1, x) = Lm (x) (2.38)
(n̄ + m)! n̄
Normalization can be done by using (Arfken 726)
Z ∞ h i2 (n̄ + k)!
dx e−x xk+1 Lkn̄ (x) = (2n̄ + k + 1) (2.39)
0 n̄!
60
2Enl ns np nd nf ng
= 1
1g
µ(Zα)2 n2 3s 2p 1f
1d
-0.25 2s
1p
-0.5
-0.75 Hydrogenic atoms
-1.0 1s
s, l = 0 p, l = 1 d, l = 2 f, l = 3 g, l = 4 h, l = 5
Figure 2.4: Hydrogenic atoms spectra 2Enl /µ(Zα)2
The final solution is, then (unfortunately several convention (see Liboff 439) have been adopted for
the Laguerre polynomials: The one adopted here Rnl ∼ L2l+1 n−l−1 , Gasiorowicz, Merzbacher, Messiah,
Liboff, Arfken, Abramowitz, AMS-55 chap. 22, etc. The other one is Rnl ∼ L2l+1 n+l of Schiff, Landau,
Pauli-Wilson, Bransden, Zettili, Tomonaga, etc. A third one is adopted by Gradshteyn)
(n − l − 1)! 4
ψnlm = Nnl e−ρ/2 ρl L2l+1
n−l−1 (ρ)Ylm |Nnl |2 =
(n + l)! n4 a3
2 (n − l − 1)! 4
Schiff −ρ/2 l 2l+1 Schiff
Schiff
ψnlm = −Nnl e ρ Ln+l (ρ)Ylm Nnl =
[(n + l)!]3 n4 a3
2
µ Zα
En = − , l < n = 1, 2, 3 · · · (2.40)
2 n
with ρ = 2x/n = 2r/na, β = 2/na, a = aµ /Z, aµ = 1/αµ, the Bohr’s radio a0 = a∞ =

1/αme = 0.529 177 208 3(19) · 10−10 m and the Rydberg energy R∞ = me α2 /2 = 13.605 691 72(53)
eV= 10 973 731.568 549(83) m−1 [4]. The degeneracy of each level can be obtained as
n−1
X n−1
X (n − 1)n
(2l + 1) = 2 l+n=2 + n = n2 (2.41)
2
l=0 l=0
Several radial wavefunctions are written bellow, for s-states

2L1n−1 (2x/n) exp[−x/n] 2 exp[−x]

Rns = 3/2
R1s = 3/2
n5/2 aµ aµ
(1 − x/2) exp[−x/2] 2(3 − 2x + 2x2 /9) exp[−x/3]
R2s = √ 3/2 R3s = 3/2
2 aµ 35/2 aµ
(4 − 3x + x2 /2 − x3 /48) exp[−x/4]
R4s = 3/2
(2.42)
16aµ
for p-states
2(2x/n)L3n−2 (2x/n) exp[−x/n] x exp[−x/2]

Rnp = √ 3/2
R2p = √ 3/2
n 5/2 n − 1 aµ
2 24 aµ
√
2 2 x(2 − x/3) exp[−x/3] x(10 − 5x/2 + x2 /8) exp[−x/4]
R3p = √ 3/2 R4p = √ 3/2
(2.43)
27 3 aµ 32 15 aµ
for d-states
2(2x/n)2 L5n−3 (2x/n) exp[−x/n]
Rnd = p 3/2
n5/2 (n2 − 4)(n2 − 1) aµ
√
2 2 x2 exp[−x/3] x2 (6 − x/2) exp[−x/4]
R3d = √ 3/2
R4d = √ 3/2 (2.44)
81 15 aµ 384 5 aµ
The formulas above can by applied to atomic systems with different degree of accuracy. A list of
atomic systems can go as follows:
1. Hydrogenic ions, with only one electron [Hadronic atoms, Rydberg atoms]. A particular case is
the one with Z large where the radiative corrections are large [Rydberg atoms]. Duterium and
tritium can be included in this category.
2. Muonic atoms [Rydberg atoms]. Are the same as above but the electron is substituted by a
muon: (Ze)µ− . They were postulated in 1947. Bohr’s formula doesn’t works for large Z due to
‘volume effects’ (a greater interaction of the muon with the nuclei), besides the usual relativistic
ones.
3. Rydberg atoms [Rydberg atoms]. Highly excited ones with n ∼ 100. In this case the radio
becomes as large as 0.1 µ m, of the size of bacterias!. The involved energies are of the order of
meV, so are not easy to study. There are two possibilities: hydrogenic ions and normal atoms
with one highly exited electron. Given that it is far from the rest of the atom it sees a nearly
Coulombic potential produced by the ‘ionic core’. These atoms are important to study the
transition from QM to Classical Mechanics.
4. Positronium (e− e+ ) and muonium (µ+ e− ) [Rydberg atoms]. They were produced by the first
time in 1951 and 1960, respectively. These atoms are a clean test of QED (no strong interactions
are involved, at least at lowest orders). Unfortunately they are unstable, although it is possible
to measure their spectra.
5. Antiatoms [Rydberg atoms]. Mainly antihydrogen (p̄e+ ): They were produced by the first time
at Cern in 2000. Other combinations have been produced like (Z = 2)e− p̄, etc. An interesting
cases are when combinations of particles and antiparticles are bounded like He++ p̄e, He++ p̄,
H+ p̄
6. Hadronic atoms [Rydberg atoms]. Examples are N π − , N K − , N p̄, N Σ− , π − π + , etc. These

atoms are mainly bounded by EM interactions with corrections due to Strong Interactions (SI).
For this reason are a good place to study SI at low energy.
7. Nuclei [15]. In this case the forces involved are the Strong Interactions, unfortunately not very
well known. The simplest case is deuterium.
8. Mesons and Quarkonium [NRQM, 4]. Again they are bounded by Strong Interactions. There
are two possibilities: mesons constituted by ‘light quarks’ (u, d and s: mu ' md ' 300 MeV
and ms ' 500 MeV) and those of ‘heavy’ quarks (c and b: mc '' 1.4 GeV and mb ' 4.5 GeV.
Quark t is not able to form bounded states due to the fact that its lifetime is too short) or
Quarkonium. Examples of the first kind are π ' ud, ¯ K ' us̄, etc. [4]. Of the second kind we
have J/ψ ' cc̄, Υ ' bb̄, Bc = bc̄, etc. [4].
System EI ν2s−1s [hz] r'a

HH̄ 13.6 eV 2.4 · 1015 0.8 Å
U 91+ 0.12 MeV 2 · 1019 8.7 mÅ=870 fm
Rydberg a. n = 100 1.4 meV 2.4 · 1011 0.8µm
Muonic a. (Nµ) 2.9 keV 5.1 · 1017 3.8 mÅ=380 fm
Ps (e− e+ ) 6.8 eV 1.2 · 1015 1.6 Å
Muonium (µ+ e− ) 13.6 eV 2.4 · 1015 0.8 Å
N π− 3.8 keV 6.7 · 1017 290 fm
π−π+ 1.9 keV 2 · 1019 570 fm
cc̄, bb̄ 200 MeV 2.4 · 1022 0.8-2.7 fm
Table 4: En = −(µ/2)(Zα/n)2 , ν2s−1s = 3(Zα)2 µ/16π~ and r = 3n2 ~c/2Zαµ.
Coulomb potential, continuous case

The radial part of the SE, for the Coulomb potential is
2
d 2 d l(l + 1) Zα
+ − + k + 2m
2
Rl = 0 (2.45)
dr2 r dr r2 r
with V = −Zα/r and k 2 = 2mE. Defining ρ = 2kr and λ = Zαm/k it becomes

2
d 2 d l(l + 1) 1 λ
+ − + + Rl = 0 (2.46)
dρ2 ρ dρ ρ2 4 ρ
Transforming to the new function Rl = ρl exp[±iρ/2]F one obtains

00 2(l + 1) λ ± i(l + 1)
F + ±i + F0 + F =0 (2.47)
ρ ρ
If now a new variable is used x = ∓iρ then

00 2(l + 1) l + 1 ∓ iλ
F + −1 + F0 − F =0 (2.48)
x x
and the solution is F = F (l + 1 ∓ iλ, 2l + 2, ∓iρ). The general solution, regular at the origin is
F = ρl [f F (l + 1 − iλ, 2l + 2, −iρ)eiρ/2 + gF (l + 1 + iλ, 2l + 2, iρ)e−iρ/2 ], but given that F (a, c, z) =
ez F (c − a, c, −z) they are not independent. The solution regular at the origin is (it can be obtained
from (2.38) by the substitution: E → −E, β → ik, ρ → 2ikr and λ → −iλ
Rkl cl ρl e−iρ/2 F (l + 1 + iλ, 2l + 2, iρ)

=
" #
e−iρ/2 −(l+1+iλ) −1−iλ eiρ/2 −(l+1−iλ) −1+iλ
Rkl → cl Γ(2l + 2) (−i) ρ + i ρ
Γ(l + 1 − iλ) Γ(l + 1 + iλ)
X 2l + 1 1 X Γ(l + 1 − iλ)
f (θ) = e2iδl − 1 Pl = (2l + 1) Pl
2ik 2ik Γ(l + 1 + iλ)
l l
Γ(l + 1 − iλ)
e2iδl = (Landau600) (2.49)
Γ(l + 1 + iλ)
giving the F (a, c, z) → (Landau d.14) defining the partial phase for the Coulomb potential as δl =
arg (Γ(l + 1 − iλ)) one has that
cl Γ(2l + 2) −λπ/2 sin (kr + λ log(kr/2) − lπ/2 + δl )

Rkl → e (2.50)
|Γ(l + 1 + iλ)| kr
and in order to obtain a plane wave, once we are far from the source:
X X sin(kr − lπ/2)
Aeikz = A (2l + 1)il jl (kr)Pl → A (2l + 1)il Pl
kr
l l
(2l + 1)il |Γ(l
+ 1 + iλ)| πλ/2 |Γ(l + 1 + iλ)| l πλ/2
cl = A e = √ ie (2.51)
Γ(2l + 2) V (2l)!
where the constant A was choosen in order to normalize the wavefunction

R∞ (Landau 141) to one, when
we have a particle in a large box of volume V and the identity 0 sin(kr) sin(k 0 r)dr = (π/2)δ(k − k 0 )
has been used. The regular wavefunction is then
X |Γ(l + 1 + iλ)|
ψ = √ il eλπ/2 (2kr)l e−ikr F (l + 1 + iλ, 2l + 2, 2ikr)Ylm (2.52)
l
V (2l)!
and (Γ(z + 1) = zΓ(z), Γ(n + 1) = n! and Γ(z)Γ(1 − z) = π/ sin(πz), |Γ(1 + iλ)|2 eπλ = 2πλ/(1 − e−2πλ )
|Γ(1 + iλ|2 1 2πλ

|Rns (0)|2 = exp(πλ) =
V V 1 − e−2πλ
0 |Γ(2 + iλ|2 k2 2πλ
|Rnp (0)|2 = exp(πλ)(2k)2 = (1 + λ2 ) (2.53)
4V V 1 − e−2πλ
2.4. SCHRÖDINGER EQ. (3D) EXERCISES 65
2.4 Schrödinger Eq. (3D) exercises

2.4.1 CM motion
1. Work out the separation between CM and relative coordinates in the case of N particles (see
Bransden AM 642 and Park).
2. Get the total energy of a diatomic molecule in a gas at temperature T . A: ET = ECM + E,
ET = (3 + 2 + 2)(kB T /2) and E = 2E0 = −2R∞ . ET = 7kB T /2 − 2R∞ .
2.4.2 Cartesian coordinates
Infinite well
3. Sketch the energy levels and their degeneracy for an infinite well in the case of, for example
2a = b = c.
4. For an an infinite well obtain expecting values of, for example x, x, xrms , x2 , x2 , vy , v, vrms , x2 ,
K, V (x) etc.
5. Obtain the order of magnitude of the energy for a particle of mass m inside a region of volume
V . Work out the cases: 1) molecule in a macroscopic box, 2) electron confined in an atom, 3)
nucleon inside a nucleia, 4) quark inside nucleon, etc.
A: In order to make an estimate one can assume the specific geometry is not very important
so one can take a cube of side a = V 1/3 . The energy levels are then given as En1 n2 n3 =
(1/2m)(π/a)2 [n21 +n22 +n23 ] ∼ (3/2m)(π/a)2 ·n2 so ∆En = (3/m)(π/a)2 n∆n. Taking n ∼ ∆n ∼ 1
∆En = (3/m)(π/a)2 · (~c)2 . Thus a) ∆En = (3/Amp )(π/a)2 ∼ (3/1 GeV)[π/1 m]2 · 0.039 (GeV ·
fm)2 ∼ 1.2 · 10−21 eV!, b) ∆En = (3/me )(π/2a0 )2 ∼ (3/0.5 MeV)[π/1 · 10−10 m]2 · 0.039 (GeV ·
fm)2 ∼ 231 eV, c) ∆En = (3/mp )(π/rN )2 ∼ (3/1 GeV)[π/1 fm]2 · 0.039 (GeV · fm)2 ∼ 1 GeV,
d) ∆En = (3/mq )(π/rN )2 ∼ (3/0.3 GeV)[π/1 fm]2 · 0.039 (GeV · fm)2 ∼ 4 GeV.
6. Show that (p − eA)n ψ = (−i∇ − eA)n ψ = (−i)n (∇ + ieA)n ψ = (−iD)n ψ (been D = ∇ − ieA,
the so called ‘covariant’ derivative) is covariant ((p − eA)n ψ → eif (p − eA)n ψ )under a ‘gauge’
transformation: eA → eA + ∇f and ψ → eif ψ, for any function f .
A: (p − eA)ψ = (−i∇ − eA)ψ → [−i∇ − eA − (∇)f ]eif ψ = eif [−i∇ + (∇f ) − eA − (∇f )]ψ =
eif [−i∇ − eA]ψ. Now one can repeat the procedure n times to show what it is asked.
7. Obtain the average energy for an ensamble of identical non interacting particles at temperature
T . The ideal gas.
A: < E >= − ∂β
∂
log Z, with β = 1/kB T . The partition function is

X
−βEn
X βπ 2 n1 2 n2 2 n3 2
Z = e = exp − + +
n n1 , n2 , n3
2m a b c
s
m3 a2 b2 c2 const.
' = 3/2 (2.54)
8π β
3 3 β
and < E >= 3kB T /2

Finite well
8. Solve the cases of ideal Quantum well (a particle confined to one dimension but free in the other
two), a Quantum wire (a particle confined in two dimensions but free in the other one) and a
Quantum dot (a particle confined in all three dimensions: a perfect box).
A:
z 2
1 1 x 2 x 2
Ekx ky n = kx2 + ky2 + nπ , Enjkz = nπ + jπ + kz2 ,
2m a 2m a b

1 x 2 y 2 z 2
Enjl = nπ + jπ + lπ (2.55)
2m a a c
9. Solve the finite potential well 3D version: V = −V0 inside the box of sides a, b and c and V = 0
outside.
Anisotropic oscillator
10. Sketch the energy levels and their degeneracy for a anisotropic harmonic oscillator in the case
of, for example ωx = ωy = ωz /2 ≡ ω/2.
11. For an anisotropic harmonic oscillator obtain expecting values of, for example x, x, xrms , x2 , x2 ,
vy , v, vrms , x2 , K, V (x) etc.
12. Solve the case of a particle in a anisotropic harmonic oscillator with a constant electric field,
V = (m/2)[ω12 x2 + ω22 y 2 + ω3 y 3 ] − eEz.
2.4.3 Central Potentials
13. Show that for central potentials such that V (r → 0) → 1/rs , with s < 2 the wavefunction
behaves as R(r → 0) → rl .
14. Show the ‘Virial Theorem’

A: The expectation value of an operator independent of time is constant so
d
0= < r · p >= i < [H, r · p] >, 2 < K >=< r · ∇V (r) > (2.56)
dt
Infinite isotropic well
15. For an an infinite isotropic well obtain expecting values of, for example x, x, xrms , x2 , x2 , vy , v,
vrms , x2 , K, V (x) etc.
16. Assuming Deuterium is a perfect bag, with a radio of 1 fm, what is the energy of the first exited
level. Do the same with the π, J/Ψ, Υ.
A: E = x2nl /2µa2 = π/mp a2 ' 0.41 GeV. a = A1/3 · 1.07 fm.
Finite isotropic well
17. For large nucleus one can use the ‘Fermi gas’ model to predict their spectra. Show that this can
explain the ‘magic numbers’(Eisberg 575, Townsend 296-7: table 10.13): Nuclei with Z and/or
N = A − Z = 2, 8, 20, 28, 50, 82, 126 are specially stable. What are the predictions assuming a
perfect bag, harmonic oscillator, finite bag, etc.
A: Perfect bag: 2, 8, 18, 20, 34, 40, 58
18. The ‘ionization’ energy of Deuterium is E1l = −2.2245 MeV (Eisberg?, Townsend?). One can
estimate its radio to be a = 1.7 fm. If one approximate the potential energy by a spherical bag,
show that V0 = 35 MeV.
√
A: Assuming c ' 2, ξ1s ' 1.89, so Enl = V0 (ξnl
2 /c2 − 1) so V = 20.6 MeV, and a = c~c/ 2µV '
0 0
2.8 fm.
19. For the 3-D isotropic harmonic oscillator show that the spectra, including the degeneracy is the
same in cartesian and spherical coordinates.
Isotropic harmonic oscillator
20. Show how an isotropic harmonic oscillator has the same spectra and degeneracy in spherical
coordinates and cartesian coordinates.
√
21. Using the ‘Virial theorem’ compute < r2 > and v ≡ vrms = < v 2 > for any state, in the case
of a isotropic harmonic oscillator.
A: 2 < p2 /2µ >=< r · µω 2 r > then < p2 >= α4 < r2 >. < E >=< p2 /2µ > +(1/2)µω 2 < r2 >
and 2µ(2n + l + 3/2)ω = α4 < r2 > +α4 < r2 >. Finally = (2n + l + 3/2)/α2 ,
< p2 >= (2n + l + 3/2)α2 , < v 2 >= (2n + l + 3/2)ω/µ and vrms = (2n + l + 3/2)ω/µ
22. For an harmonic isotropic oscillator obtain expecting values of, for example x, x, xrms , x2 , x2 ,
vy , v, vrms , x2 , K, V (x) etc.
2.4.4 Hydrogenic atoms
23. What does the periodic table become, assuming that the electromagnetic interaction energy of
the electrons can be neglected. A: 1s: 2 states: H-He, OK. 2s − 2p: 8 states: Li-Ne, OK. 3s − 3d:
10 states, wrong: real 8 states: Na-Ar. [4]
24. Deuteriom was discovered in 1932 by H. Urey (He got the 1934 Nobel Prize for this discovery)
[Hadronic atoms]. They observed that the Hα (λ = 6562.8 Å) line have a second one, due to
Deuterium shifted by 1.8 Å. Similarly the Hβ (λ = 4861.3 Å) line have a second one too, shifted
by 1.3 Å. Can you verify that the shifts are correct, assuming that Deuterium nuclei is a proton
and a neutron?.
A: ω = (µ/2)(Zα)2 [1/n21 −1/n22 ] = 2π/λ so λa /λb = µb /µa , and (∆λ/λ)Hα = (λHα −λDα )/mbdaHα =
(∆λ/λ)Hβ = me /2mp : 2.74 · 10−4 ' 2.67 · 10−4 ' 2.67 · 10−4 , that is correct!.
25. The frequency emitted in a transition 2s − 1s of the hydrogen, deuterium and muonium atoms
(2γ emission) was measured (see Th. Stöhlker et al in [Lamb], as well the 2005 Nobel prize).
Compare with our prediction from Bohr’ formula. Do the same for U92+ where ν2s−1s
LS = 468(13)
eV [Rydberg atoms]
Element νexp. [Mhz] νtheo. νtheo. [Mhz]

νH (2S1/2 − 1S1/2 ) 2466 061 413.187 103 (46) 2466 061 413.187 103(46) 2466 038 692
(νD − νH )(2S1/2 − 1S1/2 ) 670 994.334 64 (15) 670 994.334 64(15) 671 340
νµ+ e− (2S1/2 − 1S1/2 ) 2455 528 941.0(98) 2455 528 935.4(14) 2455 506 096
A: ∆E = (3µ/8)(Zα)2 = ~·2πν2s−1s , so ν2s−1s = 3me α2 /[16π(1+me /mp )~]. Similarly νD −νH =

3me α2 /(16π~)[1/(1 + me /2mp ) − 1/(1 + me /mp )]
26. ‘Quarkonium’ is a bound state of two heavy quarks QQ̄0 bounded by a potential that can be
approximate as V = −4αs /3r. Estimate αs and the radii from the energy separation between
the first two levels. For charmonium we have mJ/ψ = 3096.87 MeV y mψ(2s) = 3685.96 MeV,
while for bottomonium mΥ(1s) = 9460.3 MeV and mΥ(2s) = 10023.26 MeV. A: A. En = 2mQ −
p p
(µ/2)(4αs /3n)2 so ∆m = mQ αs2 /3 and αs = 3∆m/mQ . For Charmonium αs = 3∆m/mc =
1.2 (mc = 1.2 GeV) and aµ = 3/4αs µ = 3~c/2αs mc = 0.29 fm. For Bottomonium αs =
p
3∆m/mb = 0.6 (mb = 4.3 GeV) and aµ = 3/4αs µ = 3~c/2αs mb = 0.16 fm.
27. Compare the force between the electron and the nuclei in the hydrogen atom, with that due to
an external gravitational field le the state n = 2, for a hydrogenate atom.
28. What is the correction, if any introduced by the gravity to the hydogenic atoms by computing
the relation between Vgrav. /VCoul. .
A: Gm1 m2 /α~c ' 4.7 · 10−40 !
29. Given that the gravitational interaction has the form of the Coulomb one, compute the quantum
number n, for a macroscopic system like the earth.
A: Sun-earth: E = (mT /2)(2πr/T )2 p

− GmS mT /r ' (2.7 − 5.3) · 1033 J=-2.6 · 1033 J. Now
E = −(mT /2)(GmT mS /~cn) so n = mT c2 /2E (GmT mS /~c) ' 2.5
2
p · 10 Earth-moon: E =
74
(mL /2)(2πr/T ) −GmT mL /r ' (3.92−7.62)·10 J=-3.7·10 J. n = mL c2 /2E (GmL mT /~c) '
2 28 28
2.9 · 1068
30. Given that the gravitational interaction has the form of the Coulomb one, compute the ground
energy and the radii for the ‘atoms’: a) two black holes as heavy as the sun, b) a black hole and
the earth, c) a black hole and a proton and d) two neutrons.
A: Zα → Gm1 m2 = Gm1 m2 /~c, En = −(µc2 /2)(Gm1 m2 /~cn)2 and r = (3n2 /2) · ~c/Gm1 m2 µ
System EI r
2BH 3.6 · 10198 J 5.6 · 10−149 m
BH-E 1.9 · 10182 J 3 · 10−138 m
BH-n 2.7 · 1040 MeV 5.2 · 10−35 m
2n 9.8 · 10−69 eV 9 · 1022 m
31. Obtain ψnlm (r = 0). L1n−1 (0) = n

2 3
4 L1n−1 1 1
A: |ψnlm (r = 0)|2 = |Nn0 |2 |L1n−1 (0)|2 |Y00 |2 δl0 = √ = (2.57)
n5 a3 4π π na
and |ψnlm (r = 0)|2 = (Zαµ/n)3 /π = (Z/naµ )3 /π
√
32. Using the ‘Virial theorem’ compute < 1/r > and v ≡ vrms = < v 2 > for any state, in the
case of a hydrogen atom. A: 2 < p2 /2µ >=< r · Zα/r2 > then < p2 >= µZα < 1/r >.
< E >=< p2 /2µ > −Zα < 1/r > and −(µ/2) (Zα/n)2 =< p2 > /2µ − Zα < 1/r >. Finally
< 1/r >= Z/n2 aµ , < p2 >= (µZα/n)2 , < v 2 >= (Zα/n)2 and vrms = Zα/n
33. Show that (for s > −2l − 1, Liboff 452, Arfken p. 729, Bransden AM 610!!)
Hint: Multiply the Schrödinger equation by rs+2 R0 + crs+1 R and integrate by parts.
A: First one can show that
Z Z Z ∞
∞
00 s+2 ∞
0 0 2 s
drr R R dr = −
s+2
drr (R ) ,
s+1
drrs R0 R = − < rs−3 >
0 2 0 2
Z ∞ Z ∞ 0
1
drrs+1 R00 R = s(s + 1) < rs−3 > − drrs+1 (R0 )2 , (2.58)
0 2 0
Now multiplying the radial SE for the hydrogen atom,

2 0 2 l(l + 1) 1
Rl00 + Rl + − − Rl = 0 (2.59)
r ar r2 (na)2
by rs+2 R0 + crs+1 R one obtains
Z Z Z
∞ ∞
2 s+1 ∞
1
drr s+2
Rl00 Rl0
+2 drr +s+1
(Rl0 )2
dr r − l(l + 1)r −
s
r s+2
Rl Rl0
0 0 0 a (na)2
Z ∞ Z ∞
2 1
+c drrs+1 Rl00 Rl + 2c drrs Rl0 Rl + c < rs > −l(l + 1) < rs−1 > − < r s+1
>
0 0 a (na)2
Z ∞ Z ∞
s+2 s+1 1
=− drrs+1 (Rl0 )2 + 2 drrs+1 (Rl0 )2 − < rs−2 > + l(l + 1)s < rs−3 >
2 0 0 a 2
Z ∞
s+2 s
+ < rs−1 > +c (s + 1) < rs−3 > − drrs+1 (Rl0 )2 − cs < rs−3 >
2(na)2 2 0

2 < r s−1 >
+c <r s−2
> −l(l + 1) < r s−3
>− =0 (2.60)
a (na)2
Now one can chose c in order to eliminate the terms with Rl0 : c = −(s − 2)/2. Then
1 2s − 1 s−1
s < rs−1 > − < r s−2
> + (2l + 1) 2
− (s − 1)2
< rs−3 >= 0
(na)2 a 4
s+1 2s + 1 s
< rs > − < rs−1 > + [(2l + 1)2 − s2 ] < rs−2 >= 0 (2.61)
(na)2 a 4
and (Bransden QM 372, using the generating function)

1 l(l + 1) 2 1
< r >= 3− n a, < r2 >= 1 + 5n2 − 3l(l + 1) n2 a2
2 n 2 2

1 1 1 2 1 2
= 2 , = , = (2.62)
r n a r 2 (2l + 1)n a
3 2 r 3 l(l + 1)(2l + 1)n3 a3
−1 −2 −3
34. Obtain rnlm , rnlm and rnlm From Bethe-Salpeter, pag. 13-17.
n ν J ν+1
n+l,2l+1
< rν > = with
2Z 1
Jn+l,2l+1

s λ−µ+γ
X s
λ! γ s
σ
Jλ,µ = (−1)s−γ , σ = −(1 + s) ≤ −1
(λ − µ)!(s + 1)! µ+s−γ
r=0
s+1
It can be shown by using the Feynman-Hellman theorem, and using recurrence relations.
R∞ −ρ ρα Lk (ρ)Lk0 (ρ) (Bransden AM 610)
35. Obtain Ink,n
α
0 k0 = 0 d ρ e n n0
36. Obtain the expectation value of v = p/m (the velocity vector), for a hydrogenic atom in its
ground state.
Hint: ∇ = ûr ∂/∂r + ûθ (1/r) · ∂/∂θ + ûφ (1/r sin θ) · ∂/∂φ, and ψ1,0,0 = A exp(−r/aµ )
Chapter 3
Quantum Mechanics Formalism
3.1 Mathematical framework

3.1.1 Hilbert Spaces
1. As we have seen Quantum Mechanics is based on linear operators (like x, p = −i∇, L, H, etc.)
that in many cases do not commute, like [xi , pj ] = iδij .
2. In general these operators O are realized or represented on Hilbert spaces and are diagonalized
Oψn = λn ψn : the eigenvalues, λn and eigenvectors ψn .
P
3. A Hilbert space,
P H is then expanded by the elements or vectors ψ = n an ψn (finite or infinite)
(or |ψ >= n an |n > ‘ket’ in the Dirac notation) with arbitrary complex numbers an .
4. For each Hilbert space one can construct a Dual space constituted by the dual vectors.
5. They are defined in such that for each element ψ (or |ψ >) in H one associate a unique element
of the Dual space, noted as ψ † (or < ψ|, the ‘bra’ in the Dirac notation).
6. An scalar, inner or ‘dot’ product is defined: < ψ|φ >, or bracket in the Dirac notation.
7. Hilbert spaces are then of special interest in QM and Physics, like the following two examples
(a) Euclidean spaces, Cn , whose elements are the usual column complex vectors, |x > the
corresponding dual is the hermitian conjugate file, < x| ≡ |x >† and the inner or ‘dot’
product:
 
x1 n
X
|x > =  ...  , < x| =
 
x∗1 ··· xn , < x|y >=< x, y >= x∗k yk (3.1)
xn k=1
They are used in the Angular Momenta and spin case, for example.
(b) Functions spaces, L2 whose elements are functionsR ψ(x), the dual is the complex conjugate
and the inner product is < ψ|φ >=< ψ, φ >= ψ ∗ (x)φ(y)dµ(x), where µ(x) is a given
measure. A very common case in QM are functions like those of the Sturm-Liouville Theory
(Arfken 497, etc.) used in the previous chapters
71
72 CHAPTER 3. QUANTUM MECHANICS FORMALISM
More formally a Hilbert Space is a vectorial space (H) (with: Closure, Associativity, Null element,
inverse, linearly independent. Arfken p. 12,) with:
1. an inner or scalar product (like the cases given above) with the following properties:
(a) < ψ|φ >=< φ|ψ >∗
(b) (|ψ1 > +a|ψ2 >)† (|ψ3 > +b|ψ4 >) =< ψ1 |ψ3 > +b < ψ1 |ψ4 > +a∗ < ψ2 |ψ3 > +a∗ b <
ψ2 |ψ4 >.
(c) Norm: each element has a norm, 0 ≤ |ψ|2 =< ψ|ψ >.
i. The norm vanish for the Null vector.
ii. If the norm is one, the vector is called a unitary vector.
iii. If the inner product of two, neither of which is a null vector is zero the two vectors are
said to be orthogonal.
2. Completeness (Closure): There exists a complete set or basis: |n > such that
(a) their elements are orthogonal: < n|m >= δnm (like the usual unitary vectors in n-
dimensions, the eigenfunctions of a given operator ψn (x), etc.) and
P
(b) any element of H can be written in a unique way as |ψ >= n an |n > with an =< n|ψ >.
P
(c) An equivalent form of completeness is n |n >< n| = 1 .
(d) or in the version of functions
P R ∗
ψ(x)
P = n a n ψn (x) with an =< n|ψ >= ψm (x)ψ(x) and equivalently δ(x − y) =
n ψ n (x)ψm (y) ∗.
(e) One example is the case of the infinite potential well, where completeness means,
2X
∞ nπx nπy
sin sin = δ(x − y) (3.2)
a a a
n=1
(f) Another meaning of completeness is as follows: Every Cauchy sequence (a sequence such
that |ψn − ψl | → 0 when n and l tend to infinity) converges to an element is the space :
The Hilbert space contains all its limits .
3. One important property of the Hilbert spaces is the Schwarz inequality (Arfken 527):
| < ψ1 |ψ2 > |

| < ψ1 |ψ2 > | ≤ |ψ1 | · |ψ2 |, cos θ = (3.3)
|ψ1 | · |ψ2 |
Notice that one can define, then the ‘angle’ between any two vectors.
Proof:
(a) Let ψ = |ψ1 > +a|ψ2 >, then

(b) |ψ|2 = |ψ1 |2 + a∗ < ψ2 |ψ1 > +a < ψ1 |ψ2 > +|a|2 |ψ2 |2 ≥ 0.
(c) Choosing a = − < ψ2 |ψ1 > /|ψ2 |2 and replacing
(d) |ψ|2 = |ψ1 |2 − | < ψ1 |ψ2 > |2 /|ψ2 |2 ≥ 0 that is the Schwarz identity.
3.1. MATHEMATICAL FRAMEWORK 73
3.1.2 Operators
Now we can define operators f as a prescription by which every vector in the Hilbert space it is
associated to another one, or it is a function of the other: ψ = f φ. Special case are the Linear
operators: those that satisfy the relation f (aψ1 + bψ2 ) = af ψ1 + bf ψ2 . Antilinear Operators are those
satisfying f (aψ1 + bψ2 ) = a∗ f ψ1 + b∗ f ψ2 . Several properties are
1. The eigenvalues and eigenvectors of an operator f are defined as f ψn = fn ψn . Important cases

are
x̂|x >= x|x >, p̂|p >= p|p >, Ĥ|E >= E|E > (3.4)
and ψ(x) ≡< x|ψ >, ψ(p) ≡ (2π)3/2 < p|ψ > and ψn (x) ≡ (2π)3/2 < n|ψ >.
2. Adjoint operator, or Hermitian conjugate (f † ): It is defined as < ψ|f † |φ >=< φ|f |ψ >∗ (or
†
fnl = fln
∗ ) for any two states. It can be shown that (see exercises):
(a) the adjoint of a complex number is its complex conjugate,

(b) |ψ >† =< ψ|
(c) (f |ψ >)† =< ψ|f †
(d) (f g)† = g † f † .
(e) Transpose Operator is defined as < ψ|f T |φ >=< φ|f |ψ > (or fnl T = f ) is defined as.
ln
R
3. For
P any operator its matrix P elements are defined as fnm ≡< n|f |m >= dx ψn f ψm . f =
∗
ij |i >< i|f |j >< j| = ij fij |i >< j|

P
4. Spectral decomposition: f = n fn |n >< n| with f |n >= fn |n P
>. This is the Kernel of
the
P operator. For functions one can have F (x, y) =< x|f |y >= n fn < x|n >< n|y >=
n fn ψn (x)ψn (y). Is this possible by the Spectral Theorem by von Neuman.
∗
5. Projection operators: Defined as Pn = |n >< n|. They satisfy the following properties:
(a) Pn Pm = δnm Pn . Pn Pm = |n >< n|m >< n| = |n > δnm < n| = δnm Pn

P
(b) n Pn = 1
(c) Pn = Πj6=n [f − fj ]/[fn − fj ]
Hermitian Operators
Hermitian Operators are those such that A† = A, or in the matrix form (Anm =< n|A|m >=
∗ = f † . Other properties of Hermitian Operators are:
(< m|A|n >) = A∗mn ) and fnm = fmn nm
1. The sum of two Hermitian operators is Hermitian too.
2. The product of two Hermitian operators is Hermitian if and only if they commute. (f g)† =
g † f † = gf = f g if and only if they commute.
3. F + F † and i(F − F † ) is always Hermitian.

4. The identity, r, p, H = p2 /2m + V (r), L, etc. are hermitian.

5. Their expected values and their eigenvalues are real:
< A >=< ψ|A|ψ >=< ψ|A† |ψ >∗ =< ψ|A|ψ >∗ =< A >∗ (3.5)
QED. The second case a particular case (when |ψ > is one of its eigenvalues).
6. The eigenfunctions of a Hermitian operator are orthogonal.
Proof: Given two eigenvectors, f |n >= fn |n > and f |m >= fm |m > one can take the crossed
products < m|f |n >= fn < m|n >, < n|f |m >= fm < n|m > and subtract them to have
(fn − fm ) < m|f |n >=< m|f |n > − < m|f † |n >=< m|(f − f † )|n >= 0. Thus, if fn 6= fm the
two eigenvectors have to be orthogonal: < m|n >= 0.
7. The eigenfunction of an Hermitian operator form a complete set: Any well behaved (at least
Rb
piecewise
Pm continuous) f (x) can be approximate with
P any precision (such that limm→∞ a [f (x) −
n=0 an ψn ] 2 w(x)dx = 0)by a series like f (x) =
n an ψn . Arken 523.
8. Two commuting Hermitian operators can be diagonalized simultaneously. Proof:
(a) Let f and g be two commuting operators and f |n >= fn |n >, we have to show that
g|n >= gn |n >. Taking the combinations 0 =< m|[g, f ]|n >= (fn − fm ) < m|g|n > whose
solution has the form < m|g|n >= gn δnm . Given that < m|n >= δnm it is concluded that
< m|(g − gn )|n >= 0 and g|n >= gn |n >.
(b) The proof in the other direction goes as follows: Let |n > be a eigenvalue of f and g:
f |n >= fn |n > and g|n >= gn |n >. Now taking the combinations gf |n >= fn gn |n > and
f g|n >= fn gn |n > and subtracting them one arrive to the relation (gf − f g)|n >= 0 for
any eigenstate, thus it can be concluded they
3.1.3 Representations
A general principle is that Physical properties of a given system are determined by the commutation
relations of their dynamical variables, like canonical quantization, [pq , q] = −i. However commutation
relations do not determinate completely the operators and on the contrary there are infinite sets of
operators satisfying the commutation relations: they are the representations of the group on a given
Hilbert space. For example the following three sets of operators satisfy the [x, p] = i commutation
relations:
1. x, p = −i∇
2. p = i∇p = i ∂p
∂
,p
3.
 √   √ 
√0 1 √0 0 ··· √0 − 1 0
√ 0 ···
 1 √0 2 √0 · · ·   1 √0 − 2 0 ··· 
1 
 0 2 √0 3 ···

 iα 
 0 2
√ 

x= √  , p= √  √0 − 3 ···  (3.6)
2α
 0 0 3 0 ··· 
 2 0 0 3 0 ··· 

.. .. .. .. . . .. .. .. .. ..
. . . . . . . . . .
3.1. MATHEMATICAL FRAMEWORK 75
Unitary transformation
A unitary transformation for operators is defined as f → f 0 = U f U † , with U U † = 1 and ψ → U ψ for
vectors. It has the following properties:
1. Commutation relations are maintained: [f, g] = h becomes [f 0 , g 0 ] = h0 .
2. Expectation values do not change either
3. Any hermitian operator can be diagonalized by a unitary transformation
4. Two commuting hermitian operators are diagonalized by the same unitary transformation.
Momentum and configuration(normal) spaces

Of particular interest are the space and momenta representations, where the operators, their eigenval-
ues and their eigenfunctions are defined as: x̂|x >= x|x > and p̂|p >= p|p >. The wavefunction is then
defined as ψ(x) =< x|ψ > and ψ(p) = (2π)3/2 < p|ψ > in the space and momenta representations,
respectively. On another side < x|p̂|p >= p < x|p > and p̂ < x|p >= −i∇ < x|p >= p < x|p >, whose
solution is < x|p >= exp[ip · x]/(2π)3/2 where the normalizing condition < x|y >= δ(x − y) was used.
Thus one obtain the Fourier transformation relation
Z Z
ψ(p) = (2π)3/2 < p|ψ >= (2π)3/2 dx < p|x >< x|ψ >= dxe−ip·x ψ(x)
Z Z
dp ip·x
ψ(x) =< x|ψ >= dp < x|p >< p|ψ >= e ψ(p) (3.7)
(2π)3
Linear potential, momentum space

Another case is the linear potential (Yndurain 263) V = F x. The SE, in momentum space is (boundary
conditions)

p2 ∂
Hψ(p) = + iF ψ(p) = Eψ(p)
2m ∂p
ψ(p) = C exp[i(p3 /6m − Ep)/F ]
Z ∞
0
ψ(x) = C dp cos[px − Ep/F + p3 /6m] = π(2mF )1/3 Φ[(2mF )3/2 (x − E/F )] (3.8)
0
Harmonic oscillator, momentum space

As an example one can solve the harmonic oscillator in p-space as follows:
2
p2 1 p 1 2 ∂
2
Hψ(p) = + mω x ψ(p) =
2 2
− mω ψ(p) = Eψ(p) (3.9)
2m 2 2m 2 ∂p2
that has the same form of the Schrödinger Equation in the space representation. Taking p = αz
the equation becomes
d2 ψ
+ [λ − z 2 ]ψ = 0 (3.10)
dz 2
with λ = 2E/ω = 2mE/α2 , α2 = mω. The normalized wavefunction, in momenta space is then
(Boundary conditions in this case is that ψ(p → ±∞) = 0)
s
1
ψn (p) = √ exp[−z 2 /2]Hn (z) ≡ An exp[−z 2 /2]Hn (z) En = (n + 1/2)ω n = 0, 1, 2 . (3.11)
..
2n αn! π
Harmonic Oscillator, Matrix formulation

In order to solve the Harmonic oscillator let us define the ‘creation’ or ‘rising’ and ‘annihilation’ or
‘lowering’ operators (‘ladder’ operators) and its commutator ([x, p] = i, α2 = mω, ξ = αx)

1 iα α ip α ip
x= √ a + a† , p = √ a† − a , a= √ †
x+ 2 , a = √ x− 2 (3.12)
2α 2 2 α 2 α
and [a, a† ] = 1. The hamiltonian can be rewritten

p2 1 † 1 1
H= + mω 2 x2 = a a+ ω= N+ ω (3.13)
2m 2 2 2
where N is the hermitian ‘Number operator’ as N = a† a.
[H, a] = −ωa, [H, a† ] = ωa† , [N, a] = −a, [N, a† ] = a† (3.14)
The eigenvectors and eigenvalues of N are defined as N |n >= n|n >, and are eigenvectors and
eigenvalues of H too: H|n >= (n + 1/2)ω|n >= En |n > (En = (n + 1/2)ω). Therefore it is enough to
diagonalize N . In order to do that let us show

N a† |n > = a† N + a† |n >= (n + 1) a† |n >
N (a|n >) = (aN − a)|n >= (n − 1) (a|n >) (3.15)
so a† |n >= γn |n + 1 > (so a† is called the ‘rising’ operator), with γn a constant obtained by
normalizing
p the states:
√ < n|aa† |n >= |γn |2 =< n|a† a + 1|n >=< n|N + 1|n >= n + 1, and γn =
En /ω − 1/2 = n + 1. Doing the same for the ‘lowering’ operator it is obtained that
√ √
a† |n >= n + 1|n + 1 >, a|n >= n|n − 1 > (3.16)
Now, given that E =< H >=< p2 > /2m + mω 2 < x2 > /2 = (< N > +1/2) ω = (n + 1/2)ω ≥ 0
√
and n ≥ −1/2. Taking the ground state as |n0 > on has that a|n0 >= n0 |n0 − 1 >= 0) so n0 = 0.
Additionally n has to be integer. The reason is that if it is not, one can start with that state, |n >
3.2. QUANTUM MECHANICS FORMALISM 77
p
and by lowering enough times: a[n]+1 |n >= f a|n − [n] >= f n − [n]|n − [n] − 1 >, ending below the
ground state n0 = 0. Thus H is diagonal, and En = (n + 1/2)ω as it has to be. What happened to
the boundary conditions?, didn’t we need them?
The wavefunction, ψn (x) ≡< x|n > can be obtained too. Starting with the ground state:

α ip α 1 d
0 =< x|a|0 >=< x| √ x + 2 |0 >= √ x+ 2 ψ0 (3.17)
2 α 2 α dx
p √
so ψ0 has to satisfy the equation ψ00 = −α2 xψ0 , which solution is ψ0 = α/ π exp[−ξ 2 /2]. The
other ones can be obtained, in agreement with the Schrödinger
√ solution of eq. (1.50) by applying the
rising opertator, p.e.: ψ1 =< x|1 >=< x|a† |0 >= α/ 2 xψ0 + ψ00 /α2 , and so on. Finally the
matrix x, p and so on can be obtained, satisfying their commutation relation are given in eq. (3.6).
Easily one obtains
 √ 
1 0 − 2 0
√ ···
2 √  0 3 0 − 6 ··· 
p2 mω 2 2 1 α  − 2 
0 5 0 ··· 
H = + x =  √ 
2m 2 2m 2  0 − 6 0 7 ··· 
 
.. .. .. .. ..
. . . . .
 √ 
1 0 2 √0 · · ·
 0 3 0 6 ··· 
mω 2 1  √2 0 5 0 · · ·
 ω

+   = diag. (1, 3, 5, 7, · · · ) (3.18)
2 2α2  0 √6 0 7 ···  2
 
.. .. .. .. . .
. . . . .
3.2 Quantum Mechanics Formalism

Once the mathematical platform is settled one can construct the Physics on it, by assuming several
postulates that may be confirmed or not by testing the corresponding predictions experimentally. A
set of Postulates for Quantum Mechanics my be:
3.2.1 Postulate I
Classical Observables become Hermitian Operators, whose commutation relations are consistent with
[qi , pj ] = iδij and the result of any measurement is one of their eigenvalues.
Complete set
A set of observables is said to be Complete if a) they commute, so can be diagonalized simultaneously
b) once all the observables are diagonalized no degeneracy remains. One example is the hydrogen atom:
a complete se is given by H, L2 and Lz . An important case is the minimal set, that is the minimal
complete set needed Pto describe the system. In this case any physical state can be written as a linear
superposition ψ = n an ψn , where ψn is simultaneously eigenstate of all the observables in a minimal
complete set.
Heisenberg principle
In general for two noncommuting observables ([f, g] = ih) one has that ∆f ∆g ≥ | < h > |/2. The
proof goes as follows:
(∆f )2 ≡< ψ|(δf )2 |ψ >= |δf ψ|2 (3.19)
with δf = f − < f >. Multiplying them one obtains that
(∆f )2 (∆g)2 = |δf ψ|2 |δgψ|2 ≥ |< δf ψ|δgψ >|2 = |< ψ|δf δgψ >|2
1
= |< ψ| {δf, δg} + [δf, δg] ψ >|2
4
1 1
= |< ψ| {δf, δg} + ih|ψ >|2 ≥ | < h > |2 (3.20)
4 4
3.2.2 Postulate II
There exists a vector ψ (continuous and differentiable) containing all the physical information of the
system. Besides < f >=< ψ|f |ψ >, for any Observable. if the system is in the sate ψ the probability
to find it in the state φ is | < ψ|ψ > |.
3.2.3 Postulate III

Once one observable is measured, with value f the systems ends up (‘collapses’) in the corresponding
state |f >.
3.2.4 Postulate IV, Dynamics

The Schrödinger Picture
In the Schrödinger picture the vectors evolve in time, while the operators are constant. The time
evolution of the system is driven by the Hamiltonian: i∂|ψ(t) >S /∂t = H|ψ(t) >S and
|ψ(t) >S = exp[−itH]|ψ(0) >S ≡ U (t)|ψ(0) >S , f (t) = f (0) (3.21)
The expectation values (< f >=< ψ|f |ψ >) evolve as

d<f > ∂f
i =< [f, H] > +i (3.22)
dt ∂t
Noether’s Theorem: One can see that Constants of motion are obtained if two conditions
are satisfied: 1) [f, H] = 0, so f is the generator of a symmetry, and 2) f does not depend explicitly
of time. Examples: in the hydrogen atom H, L2 , Lz satisfy these two requirements so their quantum
numbers En , l and m are constants of motion, or conserved. On the contrary p is time independent
but do not commute with the hydrogen atom hamiltonian so it is not conserved.
Ehrenfest Theorem: The Classical Physics is a limit of the Quantum one:
3.2. QUANTUM MECHANICS FORMALISM 79

d ∂p p2
= h[p, H]i + i = p, + V (r) = h[p, V (r)]i = i h−∇V i =< F > (3.23)
dt ∂t 2m
so Newton’s second law is valid on the expectation values.
Virial Theorem:
2
d<r·p> ∂r · p p2 p
= h[r · p, H]i + i = h[r · p, H]i = i + r[p, V (r)] = i − r · [∇V (r)](3.24)
dt ∂t m m
For an stationary state d < r · p > /dt = 0 and the Viral Theorem is finally obtained
2 < K >= hr · [∇V (r)]i (3.25)
Oscillations
In the case of mixing one can have an oscillating system, X 0 ↔ X̄ 0 There are many examples like
X 0 = B 0 , D0 , Ds0 , K 0 the NH3 and polar molecules (see Townsend 111), neutrinos, etc. One can
have time dependent asymmetries. In this case the time evolution is controlled by the Schrödinger
equation

i M11 − 2i Γ11 M12 − 2i Γ12 A p2
iΨ̇ = HΨ, H = M − Γ = = ,
2 M21 − 2i Γ21 M22 − 2i Γ22 q2 A
s
q ∗ − iΓ∗ /2
M12 V ∗ Vtd
= 12
= tb ∗ = e−2iβ for q = d (3.26)
p M12 − iΓ12 /2 Vtb Vtd
with M and Γ hermitian, and CP T implies that M11 = M22 . And Their eigenvalues and eigen-
functions are

i 1 p 1 1−
HΨhl = Ehl Ψhl Ehl = A ± pq = mh,l − Γh,l Ψhl = p =p (3.27)
2 |p | + |q 2 |
2 ±q 2(1 + 2 ) ±(1 + )
with ≡ (p − q)/2p, p = 1 − and q = 1 + . The time dependant wave function is
Ψ(t) = ah e−iEh t Ψh + al e−iEl t Ψl (3.28)

For a given initial conditions at t = 0 like

1 0
Ψ(t = 0) = |X0 i = Ψ̄(t = 0) = |X̄0 i = (3.29)
0 1
The time dependant wave function is given as (for fCP = f )
q p
Ψ(t) = |X0 (t) >= g+ (t)|X0 > + g− (t)|X̄0 >, Ψ̄(t) = |X̄0 (t) >= g− (t)|X0 > +g+ (t)|X̄0 >
p q
1 −iEn t 1 1
g± (t) = (e ± e−iEl t ) = e−Γh t/2 e−iEh t [1 ± e−i∆Γt/2 e−i∆mt ] = eiAt [e−ipqt ± eipqt ] (3.30)
2 2 2
where ∆m ≡ Eh − El , ∆Γ ≡ Γh − Γl , been defined as positive
Heisenberg Picture
In this case the vectors are constant while the operators evolve in time
|ψ(t) >H = |ψ(0) >= eiHt |ψ(t) >S , fH = eiHt fS e−iHt

dfH ∂fH
i =i + [fH , H] (3.31)
dt ∂t
Time evolution of the harmonic oscillator Working in the Heisenberg representation, where
the states are constant and the operators evolve in time. According to Heisenberg
dp ∂ dx p
= − V (x) = −mω 2 x̂ = (3.32)
dt ∂x dt m
that can be decoupled and solved by writing them in the base of the ‘ladder’ operators
da da†
= −iωa, = iωa†
dt dt
a(t) = a(0)e−iωt , a† (t) = a† (0)eiωt (3.33)
So the Hamiltonian and the number operator are time independent, as they should be. The
position and momenta operators can be obtained:
p(0)
x(t) = x(0) cos ωt + sin ωt
mω
p(t) = −mωx(0) sin ωt + p(0) cos ωt (3.34)
the same of the classical case.
Interactive Picture
In this case the hamiltonian is splitted as H = H0 + HI and the vector evolve with H0 (that may be
the free part) while the operators evolve with HI (the ‘interaction’ part):
|ψ(t) >I ≡ eiH0 t |ψ(t) >S , fI = eiH0 t fS e−iH0 t

0 dfI ∂fI
|ψ(t) >I = e−iH t |ψ(0) >I , i =i + [fI , H] (3.35)
dt ∂t
and < ψ|f |ψ >I =< ψ|f |ψ >H =< ψ|f |ψ >S .
3.3 Interpretation
1. From the very begin QM interpretation in several cases has been a very controversial and difficult
topic [QM history, QM interpretation].
3.3. INTERPRETATION 81
2. From one side QM predictions have been tested at a very high level of precision like for example
the 2s−1s (2γ emission) for the hydrogen atom was measured to be ν2s−1s = 2 466 061 413 187 103(46)
hz (see ref. M. Niering, et al. in [Lamb]), Quantum Electrodynamics (QED) [23], etc. Many
more examples come from Atomic Physics (hyperfine, Raman rotational spectroscopy etc. in the
low energy range), Chemistry, Condensed matter, Quantum Optics, Particle Physics (e− e+ →
W − W + , etc. in the high energy limit at E ∼ 200 GeV [4]) etc.
3. Unfortunately this is not always the case and in many regions need to be explored or tested with
better precision.
4. Thus QM interpretation is still a controversial.
5. The most accepted interpretation is the so called Copenhagen Interpretation, but many have
never accepted it for different reasons.
6. These discussions were at the begin based on philosophical arguments and ‘gedanken experi-
ments’.
7. Fortunately as new technologies have been available it has been possible to realize several of
these almost impossible experiments and many others.
8. and sometimes fruitful topics like Quantum computation, Entangled particles, Teleportation and
so on [QM interpretation, Q Computation].
3.3.1 Copenhagen Interpretation

The so called Copenhagen QM interpretation (Park chap. 10) was due mainly to Bohr, Heisen-
berg, Born, Pauli, Jordan, Neuman, etc. The main ingredients are [Copenhagen, QM interpretation],
together with enumerate several experimental situations where interpretation has been difficult, un-
expected or controversial.
1. Take ρ = |ψ|2 as the probability density (Born-Schrödinger). ψ is symbolic not pictorial. It

can seen in particle decays and scattering, like K + decays even if the initial kaons are exactly
the same the final particles can be predicted only in a probabilistic way, as it is shown in the
accompanying table where the experimental measurements are shown.
BR R(a → b)[4] BR R(a → b) [4]

K+ → µ+ νµ 63.51 % K+ → π+π0 21.16 %
K → π+π+π−
+ 5.6 % K → π 0 µ+ νµ
+ 3.2 %
K + → π+π0π0 1.7 % K + → e+ νe 1.55 · 10−5
K + → π + µ+ µ− 8 · 10−8 K + → π + ν ν̄ 2 · 10−10
Table 1: Several Branching ratios for the K + - decay. Its lifetime is τK + = 1.2386(24) · 10−8 sec
[4].
Another place where this interpretation can be seen are in the one or more slits experiments
with one by one particle (electron, photon, neutron, etc) or with many at the same time [7, 8].
In the case of oscilations (K 0 ↔ K̄ 0 , etc. [4]) one has the same phenomena and so on.
Figure 3.1: Quamtum jumps [Bell].
2. The Heisenberg uncertainty principle, for any two nonconmuting observables.
3. Wholeness or indivisibility of Quantum states, QM is complete (Bohr-Einstein discussions). The

use of probability is not like in Statistical Mechanics but it is at a more fundamental level.
4. Complementarity or wave-particle duality (Bohr at lake Como conference in 1927). The wave-
particle duality it is illustrated by one or more slits like gratings (crystals) diffraction and
interference experiments [8, 7, Q and Classical].
5. The observer (Observers role) may affect the result of a measurement. CollapseP of the wave-
function [QM observer]. If before the measurement the wavefunction is ψ = n an ψn once the
measurement is realized and a value fn is obtained the wave function is instantaleusly projected
everywhere in the space to ψn !.
6. Correspondence principle (n → ∞), Quantum to classical [QM paradoxes, Q and Classical].

coherence and decoherence. Entanglement. Teleportantion. Quantum computation. Quantum
Cryptography. Schrödinger’s cat, etc.
Objections and discomforts to this interpretations came from Einstein, Schrödinger, DeBroglie,
etc. A short list may goes as
1. Its fundamental indeterminism
2. nolocality
3. the role of the observer
4. the uncompleteness of the theory
5. its apparent non intuitive predictions
Thus alternative interpretations have been developed to ‘explain’ the polemic points, unfortunately
arising new and even more bizarre phenomena. One can recall the Ocam’s razor principle (1285-1349):
‘It is vain to do with more what can be done with fewer’
3.3.2 Other interpretations

1. Statistical Interpretation: (see L. Ballantine in ref. [non Copenhagen, QM interpretation])
Valid for ensambles of particles.
2. Hidden Variables: (see ref. [QM interpretation, QM paradoxes, Bell]).
(a) This interpretation try to account for the determinism and uncompleteness of the theory:
The probabilistic interpretation is a consequence of QM partial description of reality. A
more complete theory including somehow unknown (by the moment) or ‘hidden’ variables
may give us a complete and deterministic description of reality.
(b) A particular case is the Bohm-DeBroglie interpretation with its ‘pilot’ wave’.
(c) This theory invoke new forces to explain the interaction between the ‘pilot’ wave and the
particles. One can recall the Ocam’s razor principle.
(d) A concrete theory of this kind was enounced by Bohm and a concrete test was propossed
by Bell as will be treated below. The experiment was realized and was not favorable to the
‘hidden’ variables ideas.
3. Many-worlds: (see B. DeWitt in ref. [non Copenhagen, QM interpretation])
4. Other interpretations: Decoherent histories (Omnes). Consistent histories (Gell-Mann, Grif-

fiths). Transactional interpretation (J. Cramer). Ithaca interpretation.
3.3.3 ‘Paradoxes’
Schrödinger’s cat
1. Formulated by Schrödinger [QM paradoxes, QM observer, Q and Classical] in 1935.
2. It arises when QM ideas are taken to the macroworld.
3. A cat is enclosed in a box in such way we can not see its interior. Inside, with the cat a radioactive
source, a trigger system and a poisson are enclosed.
4. The source has 0.5 probability of decay in a given time and of course 0.5 of not.
5. Once the decay is produced the trigger system is activate and the poisson is splited so the cat
dies.
6. The box is open after the given time and one can see the result.
7. In some sense the experiment has been done and it is in agreement with the Copenhagen inter-
pretation [Q Computation].
EPR paradox:
1. Einstein in particular express its feeling the Copenhagen interpretation was not complete and
try to find the ‘fails’ of (‘The theory yield a lot, but it hardly brings us any closer to the secret
of the Old One. In any case I am convinced that He does not throw dice’, Einsten’s letter to
Born, December 4 1926).
2. One of the ‘fails’ of the interpretation was the nonlocality (or ‘spooky action at a distance’ as
he called it) of the theory: the correlations between entangled parts of a given system separate
by timelike intervals.
3. Born and Heisenberg at the 1927 Solvay physics conference in Brussels declare QM was a com-
plete theory (‘We regard QM as a complete theory for which the fundamental physical and
mathematical hypotheses are not longer susceptible of modification’, Heisenberg and Born pa-
per at the Solvay Congress of 1927).
4. Part of Einstein’s views were published in 1935 and are known as the EPR (by Einstein, Podolsky
and Rosen ) paradox [QM paradoxes]. In the paper they ask three conditions any physical theory
has to satisfy:
(a) Locality
(b) Realism Within this line of reasoning, whether or not we can assign an element of reality to
a specific polarization of one of the systems must be independent of which measurement we
actually perform on the other system and even independent of whether we care to perform
any measurement at all on that system. To put it dramatically, one experiment could be
performed here on earth and the other on a planet of another star a couple of light years
away.
(c) Following EPR one can apply their famous reality criterion, ‘If, without in any way dis-
turbing a system, we can predict with certainty (i.e., with probability equal to unity) the
value of a physical quantity, then there exists an element of physical reality corresponding
to this physical quantity’.
(d) This would imply that to any possible polarization measurement on any one of our pho-
tons we can assign such an element of physical reality on the basis of a corresponding
measurement on the other photon of any given pair.
5. (EPR)[QM paradoxes] analyzed a thought experiment to measure position and momentum in a

pair of interacting systems.
6. Employing conventional quantum mechanics, they obtained some startling results, which led
them to conclude that the theory does not give a complete description of physical reality.
7. Their results, which are so peculiar as to seem paradoxical, are based on impeccable reasoning,
but their conclusion that the theory is incomplete does not necessarily follow.
8. Bohm simplified their experiment while retaining the central point of their reasoning; this dis-
cussion follows his account.
(a) The proton has spin 1/2; thus, no matter what direction is chosen for measuring the
component of its spin angular momentum, the values are always +1/2 or -1/2.
(b) It is possible to obtain a system consisting of a pair of protons in close proximity and with
total angular momentum equal to zero, they are entangled.
(c) Thus, if the value of one of the components of angular momentum for one of the protons
is +1/2 along any selected direction, the value for the component in the same direction for
the other particle must be -1/2.
(d) Suppose the two protons move in opposite directions until they are very far apart.
(e) The total angular momentum of the system remains zero, and if the component of angular
momentum along the same direction for each of the two particles is measured, the result is
a pair of equal and opposite values.
(f) Therefore, after the quantity is measured for one of the protons, it can be predicted for the
other proton; the second measurement is determined.
(g) As previously noted, measuring a quantity changes the state of the system. Thus, if mea-
suring Sx (the x-component of angular momentum) for proton 1 produces the value +1/2,
the state of proton 1 after measurement corresponds to Sx = +1/2, and the state of proton
2 corresponds to Sx = -1/2.
(h) Any direction, however, can be chosen for measuring the component of angular momentum.
Whichever direction is selected, the state of proton 1 after measurement corresponds to a
definite component of angular momentum about that direction.
(i) Furthermore, since proton 2 must have the opposite value for the same component, it
follows that the measurement on proton 1 results in a definite state for proton 2 relative
to the chosen direction, notwithstanding the fact that the two particles may be millions of
kilometers apart and are not interacting with each other at the time.
(j) Einstein and his two collaborators thought that this conclusion was so obviously false that
the quantum mechanical theory on which it was based must be incomplete.
(k) They concluded that the correct theory would contain some hidden variable feature that
would restore the determinism of classical physics.
9. A comparison of how quantum theory and classical theory describe angular momentum for
particle pairs illustrates the essential difference between the two outlooks.
(a) In both theories, if a system of two particles has a total angular momentum of zero, then
the angular momenta of the two particles are equal and opposite.
(b) If the components of angular momentum are measured along the same direction, the two
values are numerically equal, one positive and the other negative.
(c) Thus, if one component is measured, the other can be predicted.
(d) The crucial difference between the two theories is that, in classical physics, the system
under investigation is assumed to have possessed the quantity being measured beforehand.
(e) The measurement does not disturb the system; it merely reveals the preexisting state.
(f) It may be noted that, if a particle were actually to possess components of angular momen-
tum prior to measurement, such quantities would constitute hidden variables.
10. Does nature behave as quantum mechanics predicts?. A positive answer was given by the A.
Aspect experiments [Bell] as is going to see in the next section.
3.4 Selected Phenomenology, interpretation and applications

3.4.1 Bell inequalities
1. J. Bell ( a british physicis) [Bell, Q Computation] began by assuming the existence of some form
of hidden variable with a value that would determine whether the measured angular momentum
gives a plus or minus result.
2. He further assumed locality-namely, that measurement on one proton (i.e., the choice of the
measurement direction) cannot affect the result of the measurement on the other proton.
3. Both these assumptions agree with classical, commonsense ideas.
4. He then showed quite generally that these two assumptions lead to a certain relationship, now
known as Bell’s inequality, for the correlation values mentioned above.
5. The next step then is to assume the two entangled photons (systems) [Bell, Q Computation] to
be widely separated so that we can invoke EPRs locality assumption as given above.
6. It is this very independence of a measurement result on one side from what may be done on the
other side, as assumed by EPR, which is at variance with quantum mechanics.
7. Indeed, this assumption implies that certain combinations of expectation values have definite
bounds. The mathematical expression of that bound is called Bells inequality, of which many
variants exist.
8. Experiments have been conducted at several laboratories with photons instead of protons (the
analysis is similar), and the results show fairly conclusively that Bell’s inequality is violated.
9. An earlier experiment by Wu and Shaknov (1950) had demonstrated the existence of spatially
separated entangled states, yet failed to give data for nonorthogonal measurement directions.
10. After the realization that the polarization entangled state of photons emitted in atomic cascades
can be used to test Bells inequalities, the first experiment was performed by Freedman and
Clauser in 1972 (Fig. 6).
11. a version given by Clauser, Horne, Shimony, and Holt (1969)
12. The ones showing the largest violation of a Bell-type inequality have for a long time been the
experiments by Aspect, Grangier, and Roger (1981, 1982) in the early eighties.
13. Alain Aspect and his coworkers in Paris demonstrated this result in 1982 with an ingenious
experiment in which the correlation between the two angular momenta was measured, within a
very short time interval, by a high-frequency switching device.
14. The two photons emitted in an atomic cascade in Ca are collected with lenses and, after passage
through adjustable polarizers, coincidences are registered using photomultiplier detectors and
suitable discriminators and coincidence logic.
15. The observed coincidence counts violate an inequality derived from Bells inequality under the
fair sampling assumption.
3.4. SELECTED PHENOMENOLOGY, INTERPRETATION AND APPLICATIONS 87
16. That is to say, the observed results agree with those of quantum mechanics and cannot be
accounted for by a hidden variable (or deterministic) theory based on the concept of locality.
17. One is forced to conclude that the two protons are a correlated pair and that a measurement on
one affects the state of both, no matter how far apart they are. This may strike one as highly
peculiar, but such is the way nature appears to be.
18. It may be noted that the effect on the state of proton 2 following a measurement on proton 1 is
believed to be instantaneous; the effect happens before a light signal initiated by the measuring
event at proton 1 reaches proton 2.
19. The interval was less than the time taken for a light signal to travel from one particle to the
other at the two measurement positions.
20. Thus, there is no way that the information concerning the direction of the measurement on the
first proton could reach the second proton before the measurement was made on it. Several
results are [Bell]
S = 2.697(15), SQM = 2.70(5), −2 ≤ SOV ≤ 2

S = 0.853(9), (3.36)
where OV stands for ‘Ocult variables’ or ‘Local realism’ and the second measurement is 16
standard deviations from the OV bound.
3.4.2 Quantum Computing, Chriptography, Teleprotation, etc

There is more to information than a string of ones and zeroes the ability of ”quantum bits” to be in
two states at the same time could revolutionize information technology.
In the mid-1930s two influential but seemingly unrelated papers were published. In 1935 Einstein,
Podolsky and Rosen proposed the famous EPR paradox that has come to symbolize the mysteries
of quantum mechanics. Two years later, Alan Turing introduced the universal Turing machine in an
enigmatically titled paper, On computable numbers, and laid the foundations of the computer industry
one of the biggest industries in the world today. Although quantum physics is essential to understand
the operation of transistors and other solid-state devices in computers, computation itself has remained
a resolutely classical process. Indeed it seems only natural that computation and quantum theory
should be kept as far apart as possible surely the uncertainty associated with quantum theory is
anathema to the reliability expected from computers? Wrong. In 1985 David Deutsch introduced the
universal quantum computer and showed that quantum theory can actually allow computers to do
more rather than less. The ability of particles to be in a superposition of more than one quantum state
naturally introduces a form of parallelism that can, in principle, perform some traditional computing
tasks faster than is possible with classical computers. Moreover, quantum computers are capable
of other tasks that are not conceivable with their classical counterparts. Similar breakthroughs in
cryptography and communication followed. This quantum information revolution is described in this
special issue by some of the physicists working at the forefront of the field. Starting with the most
fundamental of quantum properties single-particle quantum interference in two-path experiments
they show how theorists and experimentalists are tackling problems that go to the very foundations of
Figure 3.2: Bell inequalities violation [Bell].
quantum theory and, at the same time, offer the promise of far-reaching applications. Anton Zeilinger
of the University of Innsbruck introduces the fundamentals of quantum information quantum bits,
entangled states, Bell-state measurements and so forth and outlines what is possible with quantum
communication. The most ambitious scheme, quantum teleportation, has recently been demonstrated
with photons and looks to be possible with atoms. The first application of teleportation is, however,
likely to be in a quantum computer or communication system rather than anything more cinematic.
Cryptography is the most mature area of quantum information and has now been demonstrated over
distances of ten of kilometres (and under Lake Geneva!). Once just the concern of special agents
and generals, cryptography now plays an important role in transactions over the Internet. On page
41 of the March issue of Physics World Wolfgang Tittel, Grgoire Ribordy and Nicolas Gisin of the
University of Geneva explain how the very properties of quantum theory that so puzzled Einstein et
al . can be used to send messages with complete security. A common theme in communication and
cryptography is that many applications work best when classical and quantum methods are used in
tandem which is why Alice and Bob, the two central characters in quantum information, are using
the telephone in the illustration. Quantum computers are a more distant proposition, but the first
logic gates have been demonstrated in the laboratory and progress is being made on three fronts:
trapped ions, photons in cavities and nuclear magnetic resonance experiments. Recent years have
also seen significant progress in the development of new algorithms for quantum computers. David
Deutsch and Artur Ekert of the University of Oxford present a progress report on page 47 and also
delve into some of the deeper implications of quantum theories of information. Of course it isn’t
all plain sailing. Quantum states are notoriously delicate and interactions with the environment can
cause a pure quantum state to evolve into a mixture of states. This causes the quantum bit to lose
two of its key properties: interference and entanglement. This process, known as decoherence, is
3.4. SELECTED PHENOMENOLOGY, INTERPRETATION AND APPLICATIONS 89
the biggest obstacle to quantum computation, as David DiVincenzo IBM and Barbara Terhal of the
University of Amsterdam explain on page 53. However, theorists have developed schemes to correct
the errors introduced by decoherence and also any inaccuracies generated by the quantum logic gates
themselves. Collaboration is a hallmark of the ever-growing quantum information community. The
European Union, for example, is funding a network of eight groups working on the Physics of Quantum
Information, while the Quantum Information and Computation collaboration in the US has been
awarded some $5 million over five years by the Department of Defense. We live in an information age
that was founded on the applications of basic physics and in which computer power continues to grow
exponentially as the feature sizes in microelectronic circuits become ever smaller. Quantum effects
can be seen as a threat or an opportunity to this growth. The quantum information technologies
described in this issue may have a very long way to go before they rival the sophistication found
in their classical counterparts but, as Deutsch and Ekert conclude, ”there is potential here for truly
revolutionary innovation”.
3.4.3 Transition from Quantum to Classical Physics

Bohr’s Correspondence principle. Decoherence an coherence. Observers role [Q and Classical].
3.4.4 Historical quotations

To interpret Quantum Mechanics is not easy as one can see from the following quotes [QM interpretation]:
1. 1815, circa. P. Laplace (1749-1827): ‘An intellect which at any given moment knows all the forces
that animate Nature and the mutual positions of the beings that comprise it, if this intellect were
vast enough to submit its data to analysis, could condense into a single formula the movement
of the greatest bodies of the universe and that of the lightest atom: for such an intellect nothing
could be uncertain; and the future just like the past would be present before its eyes’
2. 1894 A. Michelson, from his address at the dedication ceremony for the Ryerson Physical Labo-
ratory at the University of Chicago: ‘The more important fundamental laws and facts of physical
science have all been discovered, and these are now so firmly established that the possibility of
their ever being supplanted in consequence of new discoveries is exceedingly remote.... Our future
discoveries must be looked for in the sixth place of decimals’.
3. L. Kelvin, ‘There is nothing new to be discovered in physics now, All that remains is more and
more precise measurement’. He shared this sentiment at a celebration of his 50th anniversary as
professor in words that surely would have shocked his audience: ‘One word characterizes the most
strenuous of the efforts for the advancement of science that I have made perseveringly during 55
years. That word is failure. I know no more of electric and magnetic forces or of the relation
between aether, electricity and ponderable matter, or of chemical affinity than I knew and tried
to teach to my students of natural philosophy 50 years ago in my first session as professor.’
”There is nothing new to be discovered in physics now. All that remains is more and more precise
measurement.” He shared this sentiment at a celebration of his 50th anniversary as professor in
words that surely would have shocked his audience: ”One word characterizes the most strenuous
of the efforts for the advancement of science that I have made perseveringly during 55 years.
That word is failure. I know no more of electric and magnetic forces or of the relation between
aether, electricity and ponderable matter, or of chemical affinity than I knew and tried to teach
to my students of natural philosophy 50 years ago in my first session as professor.”
4. W. Pauli in the US, from a letter to R. Kronig, 25 May 1925. ‘Physics is very muddled again
at the moment; it is much too hard for me anyway, and I wish I were a movie comedian or
something like that and had never heard anything about physics!’
5. E. Schrödinger, ‘I do not like it, and I am sorry I ever had anything to do with it’.
6. N. Bohr, ‘Those who are not shocked when they first come across quantum mechanics cannot
possibly have understood it’, ‘If anybody says he can think about quantum problems without getting
giddy, that only shows he has not understood the first thing about them’.
7. Heisenberg and Max Born, paper delivered to Solvay Congress of 1927, ‘We regard quantum
mechanics as a complete theory for which the fundamental physical and mathematical hypotheses
are no longer susceptible of modification’.
8. A. Einstein: ‘Quantum mechanics is certainly imposing. But an inner voice tells me that it is
not yet the real thing. The theory says a lot, but does not really bring us closer to the secret of
the ’Old One.’ I, at any rate, am convinced that He is not playing at dice’.
9. N. Bohr reply to Einstein’s former comment: ‘Einstein, stop telling God what to do’
10. N. Bohr ‘Any one who is not shocked by quantum mechanics has not fully understood it’.
11. E. Schrödinger on Complementarity: ‘an extravaganza dictated by despair over a grave crisis’.
12. Feynman: ‘There was a time when the newspapers said that only twelve men understood the
theory of relativity. I do not believe that there ever was such a time... On the other hand, i think
is safe to say that no one understands quantum mechanics. ... Do not keep saying to yourself,
if you can possible avoid it, ’But how can it be like that?’ because you will get ’down the drain’
into a blind alley from which nobody has yet escaped. Nobody knows how it can be like that’.
13. Richard Feynman: ‘A philosopher once said ‘It is necessary for the very existence of science
that the same conditions always produce the same results’. Well, they do not. You set up the
circumstances, with the same conditions every time, and you cannot predict behind which hole
you will see the electron’
14. R. Feynman: ‘Philosophers say a great deal about what is absolutely necessary for science, and
it is always, so far as one can see, rather naive, and probably wrong’.
15. ‘Shut up and compute’; Dirac, Feynman or Mermin (see N. Mermin in [QM interpretation]),
16. Murray Gell-Mann: ‘Niels Bohr brainwashed a whole generation of physicists into believing
that the problem [of the interpretation of quantum mechanics] had been solved fifty years ago’,
Acceptance speech Noble Price (1976).
17. R. Penrose, 1986: ‘[QM] makes absolutely no sense’

3.5. FORMALISM, EXERCISES 91
3.5 Formalism, exercises

P
1. Show
P that the completeness relation can be written as n |n >< n| = 1, or δ(x − y) =
n n (x)ψm (y)
ψ ∗
P P P P
A:
P |ψ
R >= n a n |n >= n |n
R > so n |n >< Pn| = 1. ψ(x) = n an ψn (x) =
n dyψn (y)ψ(y) ψn (x) = dy [ n ψn (y)ψn (x)] ψ(y) so n ψn (x)ψm (y) = δ(x − y)
∗ ∗
R
2. Show
R that the completeness relation for the space eigenvectors is d x |x >< x| = 1 and
dp |p >< p| = 1 and is equivalent to the Fourier and inverse Fourier transforms
P
3. If ψ = n an ψn , what is the physical information contained in the an ?
4. Find out what the completeness relation means for other cases like plane wave, harmonic oscil-
lator (Arfken), Legendre Polynomials, spherical harmonics A: Liboff 767.
2X
∞ nπx nπy
sin sin = δ(x − y)
a a a
n=1
X∞
1
ein(x−y) = δ(x − y)
2π n=−∞
Z
d3 k
eik·(x−y) = δ (3) (x − y)
(2π)2
X∞
1 1 2
√ exp − (x + y 2
) Hn (x)Hn (y) = δ(x − y)
2 n n! π 2
n=1
∞
X 2l + 1
Pl (x)Pl (y) = δ(x − y)
2
l=0
X∞ m=l
X δ(θ − θ0 )δ(φ − φ0 )
[Ylm (θ, φ)]∗ Yl0 m0 (θ0 , φ0 ) = δ(Ω − Ω0 ) =
sin θ
l=0 m=−l
Z ∞
π
jl (kr)jl (kr0 )k 2 dk = δ(r − r0 ) (3.37)
0 2r2
5. Show that: i) c† = c∗ , for a complex number, ii) (f |ψ >)† =< ψ|f † , iii) (f g)† = g † f † , iv)
(f † )† = f , v) (cf )† = c∗ f † , vi) (f + g)† = f † + g † .
A:
(a) < ψ|c† |φ >=< φ|c|ψ >∗ =< ψ|c∗ |φ > and c† = c,
h i∗
(b) < φ|f |ψ >=< φ| (f |ψ >) = (f |ψ >)† |φ > =< ψ|f † |φ >∗ so (f |ψ >)† =< ψ|f † and
(c) < φ|(f g)† |ψ >=< φ|f g|ψ >∗ = ([< φ|f ] [g|ψ >])∗ = [g|ψ >]† [< φ|f ]† =< ψ|g † f † |φ > so
(f g)† = g † f †
6. Show that < x|p >= (2π)3/2 eipx .

P
Given that p̂|p >= p|p > one has < x|p̂|p >= p < x|p > and by completeness y < x|p̂|y ><
y|p >= p < x|p >. Using < x|p̂|y >=< x| − i dy
d d
|y >= −iδ(x − y) dy one has that −i dy
d
< x|p >=
p < x|p > whose solution, with the appropriated normalization the one given above.
7. Show that
(a) (|ψ >< ψ|)† = |ψ >< ψ|,

(b) Any f can decomposed into an hermitian and antihermitian part: f = H + I, with H =
(f + f † )/2 the hermitian part and I = (f − f † )/2 the antihermitian (I † = −I),
(c) if f and g are hermitian then (af + bf )† = a∗ f † + b∗ g † is hermitian if and only if a and b
are real,
(d) If f is hermitian show that the f 2 eigenvalues and the expectation values are positive for
all ψ
>, and given that the eigenvalues of f are real, their squares are positive.
A: f f † |n >= fn2 |nP
Besides < f 2 >= n |an |2 fn2 ≥ 0.
8. Show that r, p, L, Lz , L2 , the Hamiltonian, etc. are hermitian. Are xpx , xpy , xp2x , etc hermitian?
R ∗ R ∗ R ∗
A: < ψ|p† |φ >=< φ|p|ψ >∗ = dx φ∗ (−i∇)ψ = dx (i∇φ∗ )ψ = dx ψ ∗ (−i∇)φ =<
ψ|p|φ >. They are or not, given they commute or not.
9. If f is hermitian show that exp[f ] is hermitian too.

A: exp[f ] = 1 + f + f 2 /2! + f 3 /3! + · · · so (exp[f ])† = exp[f ].
10. If the states are transformed unitarity: ψ → U ψ (with U U † )
(a) What should be the transformation property for the operator O so o ≡< ψ|O|ψ > is
invariant.
(b) What happens with the relation [O1 , O2 ] = O3 , when a unitary transformation is applied?.
11. Show that E ≥ 0 for the harmonic oscillator case, using the Heisenberg uncertainty principle
(Landau 83).
12. Show that < N >= n ≥ 0

A: n =< N >=< n|a† a|n >=< ψ|ψ >≥ 0, with |ψ >≡ a|n >
13. Show that n!|n >= (a† )n |n >
14. Obtain xnm , x2nm , pnm , p2nm , etc., by using the creation and annihilation operators.
√ √
A: x = (a + a† )/ 2 α and p = −iα(a − a† )/ 2, so
3.5. FORMALISM, EXERCISES 93
1 1 √ √
xnm = < n|x|m >= √ < n|a + a† |m >= √ m < n|m − 1 > + m + 1 < n|m + 1 >
2α 2α
1 √ √
= √ m δn,m−1 + m + 1 δn,m+1
2α
1
x2nm = < n|x2 |m >= < n|a2 + (a† )2 + aa† + a† a|m >=
2α2
1 hp p i
= m(m − 1) δn,m−2 + (2m + 1)δn,m + (m + 1)(m + 2) δ n,m+2 (3.38)
2α2
15. Obtain x3nn , p3nn , x4nn and p4nn , by using the creation and annihilation operators.
√ √
A: x = (a + a† )/ 2 α and p = −iα(a − a† )/ 2, so
3
1 † 3 iα 3
x3nn = 3
< n|x |n >= √ < n|(a + a ) |n >= 0, pnn = √
3
< n|(a† − a)3 |n >= 0
2α 2
1 2 2 2 2
† †
x4nn = < n|a 2
a + a a 2
+ a† a + aa† + aa† a† a + a† aaa† |n >
4α4
1 3 1
= (n + 1)(n + 2) + n(n − 1) + n + (n + 1) + 2n(n + 1) =
2 2
n(n + 1) +
4α4 2α4 2
α 4 2 2 2 2
p4nn = < n|a2 a† + a† a2 + a† a + aa† + aa† a† a + a† aaa† |n >
4
α4
= (n + 1)(n + 2) + n(n − 1) + n2 + (n + 1)2 + 2n(n + 1)
4
3α4 1
= n(n + 1) + (3.39)
2 2
16. Is possible to measure x and px with arbitrary precision?
17. Is possible to measure Lx and Lz with arbitrary precision?
18. Is possible to measure z and pz with arbitrary precision at the same time?
19. Is possible to measure Lx and Lz with arbitrary precision at the same time?
20. Is the virial theorem valid for an arbitrary state (no necessary a pure state)?
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100 BIBLIOGRAPHY
Chapter 4
Angular Momentum
One of the most fundamental facts of nature is the observed Isotropy and homogeneity of the space
(the cosmological principle). In spite of the observed anisotropy of the Cosmic Background radiation
observed?
4.1 Orbital Angular Momentum

For an arbitrary infinitesimal rotation one has that (∆xi = (∆φ ∧ x)i = ijk ∆φj xk , see fig. 4.1)
∂ψ
ψ(r) → ψ(r + ∆ψ(r)) = ψ(r) + ∆xi = ψ(r) + iijk ri pj ψ∆φk = ψ(r) + i (Li ψ) ∆φi (4.1)
∂xi
where Li = ijk xj pk and pk = −i∂k ([xi , pj ] = iδij ). It can be shown that
[Li , xj ] = iijk xk , [Li , pj ] = iijk pk , [Li , Lj ] = iijk Lk (4.2)

and [L2 , Li ] = 0 with L2 = L2x + L2y + L2z . Spherical coordinates are more appropriate
x = r sin θ cos φ, y = r sin θ sin φ, z = r cos θ

p
r = x2 + y 2 + z 2 , cos θ = z/r, tan φ = y/x (4.3)
The Jacobian of the transformations is
   
∂r/∂x ∂r/∂y ∂r/∂z x y z
∂(r, θ, φ)  1
≡ ∂θ/∂x ∂θ/∂y ∂θ/∂z  =  cos θ cos φ cos θ sin φ − sin θ  (4.4)
∂(x, y, z) r
∂φ/∂x ∂φ/∂y ∂φ/∂x − sin φ
sin θ
cos φ
sin θ 0
(so |∂(r, θ, φ)/∂(x, y, z)| = 1/r2 sin2 θ) and the Angular momenta operators become

∂ ±iφ ∂ ∂
Lz = −i , L± = Lx ± iLy = e ± + i cot θ
∂φ ∂θ ∂φ
1 ∂ 2 1 ∂ ∂ 1
−L2 = 2 ∂φ2 + sin θ ∂θ sin θ ∂θ = − 2 (L− L+ + L+ L− ) − Lz
2
(4.5)
sin θ
101
102 CHAPTER 4. ANGULAR MOMENTUM
Figure 4.1: An infinitesimal rotation
(L2 = L± L∓ + L2z ∓ Lz ) and the commutator relations become
[L+ , L− ] = 2Lz , [Lz , L± ] = ±L± , [Lz , L2 ] = [L± , L2 ] = 0 (4.6)
4.1.1 Orbital Angular Momenta eigenvalues and Spherical harmonics

Obtain the eigenvalues of Lz is easy: one has to solve the equation
∂
Lz Φ(φ) = −i Φ(φ) = mΦ(φ) (4.7)
∂z
that has the solution Φ(φ) = aeimφ , where m is the so called ‘magnetic quantum number’. Given
that the wavefunction has a unique value for each point one has the boundary condition Φ(φ + 2π) =
Φ(φ) so m has to be an integer. Thus the normalized solution is
√
Φm (φ) = eimφ / 2π, m = 0, ±1, ±2, ±3, · · · (4.8)
Obtain the eigenvalues of L2 can be done by solving the equation (see appendix)

1 ∂2 1 ∂ ∂
L ψ=−
2
+ sin θ ψ = ν(ν + 1)ψ (4.9)
sin2 θ ∂φ2 sin θ ∂θ ∂θ
with ν a complex number. Using the method of ‘Separation of variables’: ψ = Θ(θ)Φ(φ) one
obtains
4.2. ANGULAR MOMENTA, GENERAL CASE 103
∂ ∂ m2
(1 − ξ 2 ) Θ − Θ + ν(ν + 1)Θ = 0 (4.10)
∂ξ ∂ξ 1 − ξ2
with ξ = cos θ. The general solution is θ = APνm (ξ) + BQm ν (ξ). Boundary conditions are the
finiteness of the wavefunction everywhere, in particular at ξ = ±1. The only way to satisfy it is by
taking B = 0 and ν = l = 0, 1, 2, · · · . The physical solution is then θ = APlm (ξ). Normalizing to
the whole solid angle one has the ‘Spherical Harmonics’, as the final solution
p
Lz Ylm = mYlm , L2 Ylm = l(l + 1)Ylm , L± Ylm = (l ∓ m)(l ± m + 1)Yl,m±1

2l + 1 (l − m)! 1/2
Ylm = (−1)m eimφ Plm (cos(θ))
4π (l + m)!
Z
∗
dΩYlm Yl0 m0 = δll0 δmm0 (4.11)
with l = 0, 1, 2, 3, · · · and for a given l, m = −l, −l + 1, −l + 2, · · · l. These properties are conse-

quences of the Associated Legendre Polynomials. Important properties of the spherical harmonics are
Yl,−m = (−1)m Ylm ∗ and the Parity transformation (θ → π − θ) and φ → φ + π) implies that
1/2
2l + 1 (l − m)!
Ylm → Ylm (π − θ, φ + π) = (−1)m eim(φ+π) Plm (cos(π − θ)) = eimπ (−1)l+m Ylm
(4.12)
4π (l + m)!
and P |lm >= (−1)l |lm >. Examples of the Spherical harmonics are (see polar representations in
Fig. 2)
r r r
1 3 3 ±iφ 5
Y00 = √ ; Y10 = cos θ, Y1±1 = ∓ e sin θ; Y20 = 3 cos2 θ − 1
4π 4π 8π 16π
r r
15 ±iφ 15 ±2iφ 2
Y2±1 = ∓ e sin θ cos θ, Y2±2 = e sin θ, · · · (4.13)
8π 32π
4.2 Angular Momenta, General case

4.2.1 Rotations group: SU (2) algebra
The transformation of eq. (4.1) is not the most general case because the wavefunction can be rotated
by itself (this is the case of the p. e. the electric field). The wavefunction can have components (again
as the Electric field). So in general
ψ(r) → eiφ·J ψ(r) (4.14)
where ~J are the angular momenta operators that by definition satisfy the commutation relations
[Ji , Jj ] = iijk Jk , with i, j, k = 1, 2, 3 or i, j, k = x, y, z (4.15)

a particular case is ~J = L ~ of course. But we are interested in the most general case: what are
all the possible entities satisfying commutation relation of eq. (4.15). In the mathematical language
eq. (4.15) defines an algebra and eq. (4.14) give us the corresponding group, for this particular case
SU (2) the group of rotations. What we are looking is for the irreducible representations of the SU (2)
group [1, 2]. To do that we define the ‘rising’ and ‘lowering’ operators J± ≡ Jx ± iJy
[J± , Jz ] = ∓J± , [J+ , J− ] = 2Jz , [J 2 , J± ] = [J 2 , Jz ] = 0

J 2 ≡ Jx2 + Jy2 + Jz2 = J± J∓ + Jz2 ∓ Jz = J+ J− + J− J+ + Jz2 (4.16)
4.2.2 Irreducible Representations

We are looking for the most general eigenvectors and eigenvalues of J 2 and JZ [1, 2]
J 2 |λ, m >= λ|λ, m >, Jz |λ, m >= m|λ, m > (4.17)
where the eigenvalues are real because the operators are hermitian. The eigenstates are normalized
as < λ, m|λ0 , m0 >= δλλ0 δmm0 . In the case of Orbital angular momenta the solution is |λ, m >→ Yl,m
and eqs. (4.11) is satisfied. In the general case the only thing we can assume is the commutation
relations of eq. (4.15). In order to get the representations we see that
λ =< λ, m|J 2 |λ, m >=< λ, m|Jx2 + Jy2 + Jz2 |λ, m >≥< λ, m|Jz2 |λ, m >= m2 (4.18)
so λ ≥ m2 and |m| is bounded from above. Now it can be shown that
±
J± |λ, m >= fm |λ, m ± 1 > (4.19)
where fm
± are unknown complex numbers. In order to do so first it is easy to see that
J 2 (J± |λ, m >) = λ (J± |λ, m >) (4.20)
so the vector J± |λ, m > has the same eigenvalue of J 2 as |λ, m > that means λ. Now applying the
first equation of (4.16) to |λ, m >
(J± Jz − Jz J± ) |λ, m >= ∓J± |λ, m > so

Jz (J± |λ, m >) = (m ± 1) (J± |λ, m >) (4.21)
That means the eigenvalue of Jz when applied to the vector J± |λ, m > is m ± 1 respectively. Then
eq. (4.19) is shown to be true. Given that m2 ≤ λ we define m0 (n0 ) as the maximum (minimum)
n0 +1
value of m such that J+ |λ, m0 >= 0 and J− |λ, m0 >= 0, for a given λ. Notice that n0 is a positive
integer. It can be shown that
λ = m0 (m0 + 1) = (m0 − n0 )(m0 − n0 − 1) (4.22)

The first equality follows from

0 = J− J+ |λ, m0 >= J 2 − Jz2 − Jz |λ, m0 >= (λ − m20 − m0 )|λ, m0 > (4.23)
and the second
n0 +1 n0 n0
0 = J+ J− |λ, m0 >= J+ J− J− |λ, m0 > = J 2 − Jz2 + Jz J− |λ, m0 >
n0
= λ − (m0 − n0 )2 + (m0 − n0 ) J− |λ, m0 > (4.24)
The second equation of (4.22) has two solutions for n0 : n0 = −1 and n0 = 2m0 , but only the
second is physical because n0 ≥ 0 so
n0
m0 = (4.25)
2
and from (4.22)
λ = m0 (m0 + 1) ≡ J(J + 1) (4.26)

defining J ≡ m0 we have from eq. (4.25)
J = m0 = n0 /2 = 0, 1/2, 1, 3/2, 2, · · · (4.27)

n0 +1 2m0 +1 2m0
Now m ≤ m0 = J from the relation 0 = J− |λ, m0 >= J− |λ, m0 >= J− J− |λ, m0 > ∼
J− |λ, −m0 >= 0, therefore m is bounded −m0 = −J ≤ m ≤ J = m0 and it goes from −J to J in
steps of 1. Now one can redefine the states as |λ, m >→ |Jm >, with J given by (4.27).Finally to get
±:
the unknown coefficients fm
± 2 ± 2
< Jm|J∓ J± |jm >= |fm | < J, m ± 1|J, m ± 1 >= |fm | = J(J + 1) − m2 ∓ m (4.28)
and the whole representation becomes
J 2 |Jm > = J(J + 1)|Jm >, Jz |Jm >= m|Jm >

p
J± |Jm > = J(J + 1) − m(m ± 1)|j, m ± 1 > (4.29)
Each value of J correspond to an irreducible representation of the rotations group and for a given
J, m is an integer satisfying the condition m = −J, −J + 1, · · · , J − 1, J to have self consistency. The
states are normalized as < Jm|J 0 m0 >= δJJ 0 δmm0
Spin 0, Scalars
J = 0 is the trivial representation J = m = 0 or Ji = 0. It is clear that the commutation relations
are satisfied trivially. In this case the wavefunction has only one component (the usual Schrödinger
equation) and its transformation under rotations is given by eq. (4.14). Particles with zero spin are
the pions, kaons, f0 (980), the Higgs, nuclei, atoms, etc [4].
Spin 1/2, spinors
J = 1/2 or the spinor representation. In this case m = ±1/2 and if we identify

1 0
|1/2, 1/2 >= , |1/2, −1/2 >= (4.30)
0 1
and we can see that the operators are represented by Ji = σi /2 and the Pauli matrices are

0 1 0 −i 1 0
σx = , σy = , σz = (4.31)
1 0 i 0 0 −1
and

0 1 0 0 1 1 0 3 1 0
J+ = , J− = , Jz = J =
2
(4.32)
0 0 1 0 2 0 −1 4 0 1
~ σ · B)
Properties of the Pauli Matrices: [σi , σj ] = 2iijk σk , {σi , σj } = 2δij , (~σ · A)(~ ~ =A
~ ·B
~ + i~σ ·
~ ~
(A×B), ~σ ×~σ = 2i~σ , they are traceless . In this case the wavefunction has two components

ψ1
ψ= (4.33)
ψ2
the amplitude of probability of having spin ‘up’ and spin ‘down’. This function can be seen as a
bivalued function. Its transformation law is (given that (φ·σ)2 = φ2 )

ψ(r) → eiφ·σ/2 ψ(r) = [cos(φ/2) + in̂ · σ sin(φ/2)] ψ(r) ≡ d1/2 ψm0
mm0

cos(β/2) − sin(β/2)
d1/2 (β) ≡ e−iσ2 β/2 = (4.34)
sin(β/2) cos(β/2)
where φ is the magnitude of the rotation angle and n̂ is a unitary vector in along the rotation
angle (see Rose 52 for Euler angles in this context). Notice that for the case of a 2π rotation the
wavefunction gain a minus sign ψ(~r) → −ψ(~r), later we will see that is possible to detect this minus
sign in neutron interferometry (see Sakurai 162-3 in ref. [3]. The eigenvalues of the Spin operator, for
a general rotation around the axis define by the unit vector n̂ are

nz n−
σ · n̂χ1,2 (n̂) = χ1,2 (n̂) = ±χ1,2 (n̂) (4.35)
n+ −nz
with

1 + nz cos(θ/2) −n− − sin(θ/2) e−iφ
χ1 (~n̂) = N1 = , and χ2 (~n̂) = N2 = (4.36)
n+ sin(θ/2) eiφ 1 + nz cos(θ/2)
where n± = nx ± iny , |N1 |2 = |N2 |2 = 1/2(1 + nz ) = 1/4 cos2 (θ/2) and the eigenvectors are
orthonormalized: χ†i χj = δij .
Electron spin was proposed by the first time by Compton in 1921, imagining the electron as small
sphere spining around itself to produce its magnetic dipole moment. This model can be easily shown
to produce equatorial speeds, for the electron greater than c (see exercises). Given that experimentally
re < 10−19 m. However it was discovered by Stern and Gerlach in 1922 (obtaining the Nobel prize
in 1943)[4]. Later on S. Goudsmit and U. Uhlenbeck [3] (1925) introduce electron spin to explain
fine structure lines (fine structure) and the anomalous Zeeman effect, that were not explained by the
Sommerfelds theory (see Eisberg in ref. [2]). It was incorporated to the SE in 1927 by Pauli, obtaining
the Pauli equation. The electron magnetic momenta was measured by the first time by Phipps and
Taylor in 1927 [4]. Examples of particles with spin 1/2 are leptons (e− , positron, neutrinos, µ± , etc.)
quarks, proton, neutron (the constituents of terrestrial matter), nucleia, atoms, etc [4].
Spin 1, Vectors
J = 1 or vector representation. In this case m = 0, ∓1 and the vector can be identify with
    
1 0 0
|1, 1 >=  0  , |1, 0 >=  1  , |1, −1 >=  0  , (4.37)
0 0 1
and the operators are represented by the matrices J 2 = 2
     
√ 0 1 0 √ 0 0 0 1 0 0
J+ = 2  0 0 1  , J− = 2  1 0 0  , Jz =  0 0 0 
0 0 0 0 1 0 0 0 −1
   
0 1 0 0 −i 0
1 1 1 1
Jx = (J+ + J− ) = √  1 0 1  , Jy = √ (J+ − J− ) = √  i 0 −i  (4.38)
2 2 2 i 2
0 1 0 0 i 0
as before (Sakurai 195)
 √ 
1 + cos β − 2 sin β 1√− cos β
1 √
d(1) =  2 sin β √ 2 cos β − 2 sin β
 (4.39)
2
1 − cos β 2 sin β 1 + cos β
Particles having spin one are the gauge bosons or mediators in the Standard Model: photon (for
EM), W ± , Z (for Weak interactions), gluons (for Strong interactions), ρ(770), nucleia, atoms, etc [4].
Spin 3/2
J = 3/2
 √   √ 
√0 3 0 0 0
√ − 3 0 0
1 3 0 2 √0  
 , Jy = i  3 0 −2 0 
Jx =  
√  (4.40)
2 0 2 √0 3 2 0 2 √0 − 3

0 0 3 0 0 0 3 0
Jz = diag.(3/2, 1/2, −1/2, −3/2) and J 2 = (15/4). Examples of particles with spin 3/2 are the
decuplet of barions: ∆(1232), Σ(1385), Ξ(1530) and Ω(1672), nuclei, atoms, etc.
4.2.3 Sum of Angular Momentun

The problem now is to add two o more angular momenta, what is the meaning of J = J1 + J2 ?. For
example in the simplest atom, the hydrogen one has to add the orbital angular momenta with the spins
of the electron and the proton. We have seen how J12 and J1z (J22 and J2z ) are diagonal if we use the
base |j1 m1 ) (|j2 m2 >). The number of independent states in these bases is (2J1 +1)·(2J2 +1), because
they are independent. However J 2 = (J1 + J2 )2 is not diagonal in this base, because [J 2 , J1z ] 6= 0
(or equivalentely [J 2 , J2z ] 6= 0). We have then to find a new base in wich J 2 and Jz = J1z + J2z are
diagonals. Given that J12 and J22 conmute between themselves and with J 2 and Jz we can diagonalize
all the four operator. The new base is then charaterized by their quantum numbers |Jm; J1 J2 >, so
J 2 |Jm; J1 J2 >= J(J + 1)|Jm; J1 J2 >

Jz |Jm; J1 J2 >= m|Jm; J1 J2 >
J12 |Jm; J1 J2 >= J1 (J1 + 1)|Jm; J1 J2 >
J22 |Jm; J1 J2 >= J2 (J2 + 1)|Jm; J1 J2 > (4.41)
It can be shown that J can take only the values
J = J1 + J2 , J1 + J2 − 1, · · · , |J1 − J2 | (4.42)
and for each value of J, m = −J, −J + 1, · · · , J, as it should be. To illustrate it we can contract
the table. By applying Jz = J1z +J2z to the eigenvalues of eq. (4.46) one get that m = m1 +m2 . From
that we see that m is between a minimum of mmin. = −J1 − J2 and a maximum of mmin. = J1 + J2 .
For the maximum value of m we have only one state: that one with m1 = J1 and m2 = J2 , so the
only possibility for J is J = J1 + J2 (its maximum value). For the next case, m = J1 + J2 − 1 there
are two states: (m1 = J1 − 1, m2 = J2 ) and (m1 = J1 , m2 = J2 − 1), so now J can have two values:
J = J1 + J2 and J = J1 + J2 − 1. These analysis can be followed, with the consequent increasing of
one state in each step. At some point we will find that m = J1 − J2 (given that J1 ≥ J2 ) when the
number of states is maximum, 2J2 + 1. Then the possible values of J are J1 + J2 , J1 + J2 − 1, · · · ,
J1 − J2 , that means (J1 + J2 ) − (J1 − J2 ) + 1 = 2J2 + 1. J then can not decrease anymore because we
will have more states (for a given m) in the base |Jm, J1 J2 > than in the base |J1 m1 > |J2 m2 >. All
this is better illustrate in the following table for a given example.
m Base (m1 , m2 ) Base |J, m > Numb. of states

3/2 (1/2, 1) J = 3/2 1 state
1/2 (1/2, 0) (−1/2, 1) J = 3/2, 1/2 2 states
(4.43)
−1/2 (1/2, −1) (−1/2, 1) J = 3/2, 1/2 2 states
−3/2 (−1/2, −1) J=3/2 1 states
6 states 6 states
Table 1: J = 1/2 + 1 = 1/2, 3/2. The total number of states is 6 = (2 · (1/2) + 1) · (2 · 1 + 1)


4 (1, 3) J =4 1 state
3 (1, 2) (0, 3) J = 4, 3 2 states
2 (1, 1) (0, 2) (−1, 3) J = 4, 3, 2 3 states
1 (1, 0) (0, 1) (−1, 2) J=4,3,2 3 states
0 (1, −1) (0, 0) (−1, 1) J=4,3,2 3 states (4.44)
−1 (1, −2) (0, −1) (−1, 0) J=4,3,2 3 states
−2 (1, −3) (0, −2) (−1, −1) J=4,3,2 3 states
−3 (0, −3) (−1, −2) J=4,3 2 states
−4 (−1, −3) J=4 1 states
21 states 21 states
Table 2: J = 1 + 3 = 2, 3. The total number of states is 21 = (2 · 1 + 1) · (2 · 3 + 1)
It can be shown that the number of states in the base |J, m > is (2J1 + 1)(2J2 + 1) too. For each J
there are 2(J1 + j2 ) + 1 states, and taken into account that J goes from J = |J1 − J2 | to J = J1 + J2
in steps of 1, we have the total number of states is
[2(J1 + J2 ) + 1] + [2(J1 + J2 − 1) + 1] + · · · + [2|J1 − J2 | + 1]

2J2
X 2J2
X
= [2(J1 + J2 − k) + 1] = [2(J1 + J2 ) + 1] (2J2 + 1) − 2 k
k=0 k=0
= [2(J1 + J2 ) + 1] (2J2 + 1) − 2J2 (2J2 + 1)
= (2J2 + 1) [2(J1 + J2 ) + 1 − 2J2 ] = (2J2 + 1)(2J1 + 1) (4.45)
4.2.4 Clebsch-Gordan Coefficients

Given that the new base has to have the same number of states, one can transform back and forth
between the two bases by using the relations
X
|Jm; J1 J2 >= < J1 m1 ; J2 m2 |Jm; J1 J2 > |J1 m1 > |J2 m2 >
m1 m2
X
|J1 m1 > |J2 m2 >= < Jm; J1 J2 |J1 m1 ; J2 m2 > |Jm; J1 J2 > (4.46)
Jm
where < J1 m1 ; J2 m2 |Jm; J1 J2 > and < Jm; J1 J2 |J1 m1 ; J2 m2 > are the Clebsch-Gordan coeffi-
cients. A few of them are given in the table, but in general can be obtained by using for example
Mathematica. The notation is not unique, for example Landau in ref. [1]

J1 J2 J √
< J1 m1 ; J2 m2 |Jm; J1 J2 >= (−1)J1 −J2 +m 2J + 1 = CJJm
1 m1 ;J2 m2
m1 m2 m
(4.47)
so eq. (4.46) can be written as

X
J1 J2
ψJm = CJJm ψ ψ
1 m1 ;J2 m2 J1 m1 J2 m2
m1 m2
X
ψJ1 m1 ψJ2 m2 = CJJm ψ J1 J2
1 m1 ;J2 m2 Jm
(4.48)
Jm
The calculation of the Clebsch-Gordan coefficients can be done by using the properties of the
operators and the eigenvectors (see Schiff in ref. [1], and [1, 2].
Clebsch-Gordan Coefficients. Example: 1/2 + 1/2

In this case J = 1, 0
J =1: 11
|11 >= C1/21/2,1/21/2 |1/2, 1/2 > |1/2, 1/2 >= |1/2, 1/2 > |1/2, 1/2 >
10
|10 >= C1/21/2,1/2−1/2 |1/2, 1/2 > |1/2, −1/2 > +C1/2−1/2,1/21/2
10
|1/2, −1/2 > |1/2, 1/2 >
1
= √ (|1/2, 1/2 > |1/2, −1/2 > +|1/2, −1/2 > |1/2, 1/2 >)
2
|1 − 1 >= C1/2−1/2,1/2−1/2
1−1
|1/2, −1/2 > |1/2, −1/2 >= |1/2, −1/2 > |1/2, −1/2 >
J =0: 00
|10 >= C1/21/2,1/2−1/2 |1/2, 1/2 > |1/2, −1/2 > +C1/2−1/2,1/21/2
00
|1/2, −1/2 > |1/2, 1/2 >
1
= √ (|1/2, 1/2 > |1/2, −1/2 > −|1/2, −1/2 > |1/2, 1/2 >)
2
(4.49)
Several comments are in order.
1. The wavefunction is symmetric for the case of J = 1 and antisymmetric if J = 0.
2. For J = 1 we have three states (a triplet) while for J = 0 only one state is obtained (singlet).
3. One important phenomena explained by this example is the Hyperfine Structure, let’s see.
(a) For the hydrogen atom we have that this is the case, where we have to add the spins of the
electron and proton.
(b) It happens that the base state is splitted in two new states: one degenerate triplet, with
(J = 1) and one singlet with (J = 0), the new base state.
(c) The transition between these two levels is possible and is the famous 21 cms line (the most
abundant in the universe) [hyperfine].
(d) Its best experimental value is ν = 1420.405 751 766 7(10) Mhz [hyperfine, 23], one of the
best known number in Physics.
(e) This line was predict by H. van Hulst and Oort as a possible tool to study the center of
our galaxy and was detected by the first time by Ewen and Purcell in 1951 [hyperfine].
(f) Hydrogen line observations soon produced the first maps of our galaxy’s spiral arms, until
then hidden from human view by dust; they have been a major tool of radioastronomy ever
since.
35. Clebsch-Gordan coefficients 1
35. CLEBSCH-GORDAN COEFFICIENTS, SPHERICAL HARMONICS,

AND d FUNCTIONS
p J J . ..
Note: A square-root sign is to be understood over every coefficient, e.g., for −8/15 read − 8/15. Notation:
M M . ..
r m1 m2
1/2 × 1/2 1
+1 3
1 0 Y10 = cos θ 2× 1/2 + 5/2 m 1 m 2 Coefficients
+ 1/2 + 1/2 1 0 0 4π 5/2 5/2 3/2
r + 2 +1/2 1 + 3/2 + 3/2
. .
+ 1/2 − 1/2 1/2 1/2 1
− 1/2 + 1/2 1/2 − 1/2 − 1
3 . .
Y11 = − sin θ eiφ + 2 − 1/2 1/5 4/5 5/2 3/2 . .
− 1/2 − 1/2 1 8π + 1 + 1/2 4/5 − 1/5 + 1/2 + 1/2
r
5 3 1 + 1 − 1/2 2/5 3/5 5/2 3/2
Y20 = cos2 θ − 0 + 1/2 3/5 − 2/5 − 1/2 − 1/2
1× 1/2 3/2 4π 2 2
+ 3/2 3/2 1/2 r 0 − 1/2 3/5 2/5 5/2 3/2
+ 1 + 1/2 1 + 1/2 + 1/2
15 − 1 + 1/2 2/5 − 3/5 − 3/2 − 3/2
Y21 = − sin θ cos θ eiφ
+ 1 − 1/2 8π 2 − 1 − 1/2 4/5 1/5 5/2
1/3 2/3 3/2 1/2
r 3/2× 1/2 + 2 2 1 − 2 + 1/2 1/5 − 4/5 − 5/2
0 + 1/2 2/3 − 1/3 − 1/2 − 1/2
1 15 + 3/2 +1/2 1 + 1 + 1
0 − 1/2 Y2 =
2 sin θ e
2 2iφ − 2 − 1/2 1
− 1 + 1/2
2/3 1/3 3/2
1/3 − 2/3 − 3/2
4 2π + 3/2 − 1/2 1/4 3/4 2 1
+ 1/2 + 1/2 3/4 − 1/4 0 0
2×1 3
+3 3 2
− 1 − 1/2 1
3/2 × 1 + 5/2 + 1/2 − 1/2 1/2 1/2 2 1
5/2 5/2 3/2
+2 +1 1 +2 +2 + 3/2 + 1 1 + 3/2 + 3/2 − 1/2 + 1/2 1/2 − 1/2 − 1 − 1
+ 2 0 1/3 2/3 3 2 1 + 3/2 0 2/5 3/5 5/2 3/2 1/2 − 1/2 − 1/2 3/4 1/4 2
+ 1 + 1 2/3 −1/3 +1 +1 +1 + 1/2 + 1 3/5 − 2/5 + 1/2 + 1/2 + 1/2 − 3/2 + 1/2 1/4 − 3/4 − 2
+ 2 −1 1/15 1/3 3/5 + 3/2 − 1 1/10 2/5 1/2 − 3/2 − 1/2 1
1× 1 + 2 2 1 + 10 + 01 8/15
2 1/6 − 3/10
2/5 − 1/2 1/10
3 2 1 + 1/2 0 3/5 1/15 − 1/3 5/2 3/2 1/2
0 0 0 − 1/2 + 1 3/10 − 8/15 1/6 − 1/2 − 1/2 − 1/2
+1 +1 1 +1 +1
+ 1 − 1 1/5 1/2 3/10 + 1/2 − 1 3/10 8/15 1/6
+ 1 0 1/2 1/2 2 1 0 0 0 3/5 0 − 2/5 3 2 1 − 1/2 0 3/5 − 1/15 − 1/3 5/2 3/2
0 + 1 1/2 − 1/2 0 0 0 − 1 + 1 1/5 − 1/2 3/10 −1 −1 −1 − 3/2 + 1 1/10 − 2/5 1/2 − 3/2 − 3/2
+ 1 − 1 1/6 1/2 1/3 0 − 1 2/5 1/2 1/10 − 1/2 − 1 3/5 2/5 5/2
0 0 2/3 0 − 1/3 2 1 − 1 0 8/15 − 1/6 − 3/10 3 2 − 3/2 0 2/5 − 3/5 − 5/2
− 1 + 1 1/6 − 1/2 1/3 − 1 − 1 − 2 + 1 1/15 − 1/3 3/5 − 2 − 2 − 3/2 − 1 1
0 − 1 1/2 1/2 2 − 1 − 1 2/3 1/3 3
Y`−m = (−1)m Y`m∗ − 1 0 1/2 − 1/2 − 2 r − 2 0 1/3 − 2/3 − 3 hj1 j2 m1 m2 |j1 j2 JM i
−1 −1 1 4π −2 −1 1
d `m,0 = Y m e−imφ = (−1)J−j1 −j2 hj2 j1 m2 m1 |j2 j1 JM i
2` + 1 `
j 0 j
d m0 ,m = (−1)m−m d m,m0 = d −m,−m0
j 3/2 × 3/2 3
+3 3 1/2 θ 1 + cos θ
2 d 10,0 = cos θ d 1/2,1/2 = cos d 11,1 =
+ 3/2 + 3/2 1 +2 +2 2 2
2 × 3/2 + 7/2 + 3/2 + 1/2 1/2 1/2 3 2 1 1/2 θ 1 = − sin θ
7/2 7/2 5/2
+ 1/2 + 3/2 1/2 − 1/2 + 1 + 1 +1 d = − sin d 1,0 √
+ 2 + 3/2 1 + 5/2 + 5/2
1/2,−1/2 2 2
+ 3/2 − 1/2 1/5 1/2 3/10
+ 2 + 1/2 3/7 4/7 7/2 5/2 3/2 + 1/2 + 1/2 3/5 0 − 2/5 1 − cos θ
+ 1 + 3/2 4/7 − 3/7 + 3/2 + 3/2 + 3/2 − 1/2 + 3/2 1/5 − 1/2 3/10
3 2 1 0
d 11,−1 =
0 0 0 0 2
+ 2 − 1/2 1/7 16/35 2/5 + 3/2 − 3/2 1/20 1/4 9/20 1/4
+ 1 +1/2 4/7 1/35 − 2/5 7/2 5/2 3/2 1/2
+ 1/2 − 1/2 9/20 1/4 − 1/20 − 1/4
2×2 4
+4 4 3
0 +3/2 2/7 − 18/35 1/5 + 1/2 + 1/2 + 1/2 + 1/2 − 1/2 + 1/2 9/20 − 1/4 − 1/20 1/4 3 2 1
+ 2 − 3/2 1/35 6/35 2/5 2/5 − 3/2 + 3/2 1/20 − 1/4 9/20 − 1/4 − 1 − 1 −1
+2 +2 1 +3 +3
+ 1 − 1/2 12/35 5/14 0 − 3/10 + 1/2 − 3/2 1/5 1/2 3/10
+2 +1 1/2 1/2 4 3 2 0 +1/2 18/35 − 3/35 − 1/5
+1 +2 1/2 − 1/2 + 2 +2 +2
1/5 7/2 5/2 3/2 1/2 − 1/2 − 1/2 3/5 0 − 2/5 3 2
− 1 +3/2 4/35 − 27/70 2/5 − 1/10 − 1/2 − 1/2 − 1/2 − 1/2 − 3/2 + 1/2 1/5 − 1/2 3/10 − 2 − 2
+ 2 0 3/14 1/2 2/7 + 1 − 3/2 4/35 27/70 2/5 1/10
+ 1 +1 4/7 0 − 3/7 − 1/2 − 3/2 1/2 1/2 3
4 3 2 1 0 − 1/2 18/35 3/35 − 1/5 − 1/5
0 +2 3/14 − 1/2 2/7 +1 +1 +1 +1 − 1 +1/2 12/35 − 5/14 0 3/10 7/2 5/2 3/2
− 3/2 − 1/2 1/2 − 1/2 − 3
+ 2 − 1 1/14 3/10 3/7 1/5 − 2 +3/2 1/35 − 6/35 2/5 − 2/5 − 3/2 − 3/2 − 3/2 − 3/2 − 3/2 1
+ 1 0 3/7 1/5 − 1/14 − 3/10 0 − 3/2 2/7 18/35 1/5
0 +1 3/7 − 1/5 − 1/14 3/10 4 3 2 1 0 − 1 − 1/2 4/7 − 1/35 − 2/5 7/2 5/2
− 1 +2 1/14 − 3/10 3/7 − 1/5 0 0 0 0 0
− 2 + 1/2 1/7− 16/35 2/5 − 5/2 − 5/2
+ 2 − 2 1/70 1/10 2/7 2/5 1/5 − 1 − 3/2 4/7 3/7 7/2
+ 1 − 1 8/35 2/5 1/14 − 1/10 − 1/5 − 2 − 1/2 3/7 − 4/7 − 7/2
0 0 18/35 0 − 2/7 0 1/5
− 1 +1 8/35 − 2/5 1/14 1/10 − 1/5 4 3 2 1 − 2 − 3/2 1
3/2 1 + cos θ θ − 2 +2 1/70 − 1/10 2/7 − 2/5 1/5 −1 −1 −1 −1
d 3/2,3/2 = cos
2 2 + 1 − 2 1/14 3/10 3/7 1/5
√ 1 + cos θ 1 + cos θ 2 0 − 1 3/7 1/5 − 1/14 − 3/10
3/2 θ d 22,2 = − 1 0 3/7 − 1/5 − 1/14 3/10
d 3/2,1/2 =− 3 sin 2
4 3 2
2 2 − 2 +1 1/14 − 3/10 3/7 − 1/5 −2 −2 −2
√ 1 − cos θ θ 1 + cos θ 0 − 2 3/14 1/2 2/7
3/2
d 3/2,−1/2 = 3 cos d 22,1 = − sin θ − 1 − 1 4/7 0 − 3/7
2 2 2 4 3
√ 1 + cos θ − 2 0 3/14 − 1/2 2/7 − 3 − 3
3/2 1 − cos θ θ 6 d 21,1 = (2 cos θ − 1)
d 3/2,−3/2 = − sin d 22,0 = sin2 θ − 1 − 2 1/2 1/2 4
2 2 4 2 − 2 − 1 1/2 − 1/2 − 4
r
3/2 3 cos θ − 1 θ 1 − cos θ 3 −2 −2
d 1/2,1/2 = cos d 22,−1 = − sin θ d 21,0 = − sin θ cos θ 1
2 2 2 2
3 cos θ + 1 θ 1 − cos θ 2 1 − cos θ 3 1
3/2
d 1/2,−1/2 = − sin d 2,−2 =
2 d 1,−1 =
2 (2 cos θ + 1) d 20,0 = cos2 θ −
2 2 2 2 2 2
Figure 35.1: The sign convention is that of Wigner (Group Theory, Academic Press, New York, 1959), also used by Condon and Shortley (The
Theory of Atomic Spectra, Cambridge Univ. Press, New York, 1953), Rose (Elementary Theory of Angular Momentum, Wiley, New York, 1957),
and Cohen (Tables of the Clebsch-Gordan Coefficients, North American Rockwell Science Center, Thousand Oaks, Calif., 1974). The coefficients
here have been calculated using computer programs written independently by Cohen and at LBNL.
Figure 4.2: Clebsh-Gordan coefficients. Taken from PDG at wwww.lbl.gov

4. Another case is the hydrogen molecule, that constitutes the normal gas. This is a diatomic
molecule with two electrons with their corresponding spins (the nuclei spins are smaller), that
again have to be added to get one degenerate triplet (orthohydrogen) and one singlet (parahy-
drogen).
Clebsch-Gordan Coefficients. Example: 1 + 1/2

In this case J = 1/2, 3/2. But let’s obtain the |J1 , m1 > |J2 , m2 > and change the notation:
1/2 3/2 1/2

p 3/2
p 1/2
φ11 φ1/2 = φ3/2 φ11 φ−1/2 = 1/3 φ1/2 + 2/3 φ1/2
1/2
p 3/2
p 1/2 1/2
p 3/2
p 1/2
φ10 φ1/2 = 2/3 φ1/2 − 1/3 φ1/2 φ10 φ−1/2 = 2/3 φ−1/2 + 1/3 φ−1/2
1/2
p 3/2
p 1/2 1/2 3/2
φ1−1 φ1/2 = 1/3 φ−1/2 − 2/3 φ−1/2 , φ1−1 φ−1/2 = φ−3/2 (4.50)
4.2.5 Wigner-Eckart Theorem

In general an operator transforms under an infinitesimal rotation (with U (δθ) = exp[iJ · δθ]) as
A → U † (δθ)AU (δθ) → A + iδθ[A, n · J] (4.51)
for a vector A → A + iδθ ∧ A

Scalar operator [Ji , S] = 0, Vector operator [Ji , Vj ] = iijk Vk . Tensor of second rank, for example
Tij = Ai Bj , with A and B vector operators. it can be decomposed as
(0) (1) (2)

Tij = Tij + Tij + Tij
(0) 1 (1) 1 (2) 1 (0)
Tij = Tll δik , Tij = (Tij − Tji ) , Tij = (Tij + Tji ) − Tij (4.52)
3 2 2
For a tensor Tqk (Merzbacher 401).
< n0 j 0 m0 |Tqk |njm >=< jm| < kq|j 0 m0 ; jk >< n0 j 0 |T k |nj > (4.53)
Examples are: for an scalar field
< jm|S|j 0 m0 >=< j|S|j > δjj 0 δmm0 (4.54)
For a vector
1
< jm|Aq |j 0 m0 >= < jm|J · A|j 0 m0 >< jm|Jq |j 0 m0 > (4.55)
j(j + 1)
4.3. APLICATIONS 113
4.3 Aplications
4.3.1 Raman Spectroscopy (Molecular Rotation)
1. The Hamiltonian for an arbitrary rotating body
" #
1 L2x L2y L2z
Hrot. = + + (4.56)
2 Ix Iy Iz
where Ii is the Inertia Momenta around the ith -main axis.
2. For the case of the sphere one has that all the momenta of inertia are equal and Hsphere = L2 /2I.
(a) Thus the Schrödinger equation can be easily solved to obtain
l(l + 1)
El = , ψ = Ylm (4.57)
2I
(b) In this case each state has a degeneracy of 2l + 1 states.
3. For a semi-symmetric body, with Ix = Iy 6= Iz one has that
" #
1 L2x + L2y L2z 1 2
Hrot. = + = L + (Ix /Iz − 1) L2z (4.58)
2 Ix Iz 2Ix
(a) and the solution is
1
Elm = l(l + 1) + (Ix /Iz − 1) m2 , ψ = Ylm (4.59)
2Ix
4. The general case (I1 6= I2 6= I3 ) is more difficult (see Davidov in ref. [1]).
(a) It doesn’t have any analytic solution and it has to be treated perturbatively
Effect ∆E [eV] ν [hz] ν̄ [cm−1 ] λ T [o K] range

Electr. 1 1014 1 µm 12000 Optic/ultraviolet
Vibrat. 0.03 1013 103 − 104 40 µm 350 Infrared
Rotat. 10−3 1011 1 − 102 1.2 mm 12 Infrared/microwave
Table 3: Molecular spectra. Main contributions.
1. The roto-vibrational molecular spectra (see Fig. 3) has

p several parts (a more rigorous treat-
ment is given in terms of the expansion in powers of me /M , given by the theory of Born-
Oppenheimer in 1928. See Bransden AM chap. 9, French and Taylor 487-500, Eisberg 461-471,
Townsend 254, Park 202):
Figure 4.3: Raman spectroscopy
2. The electronic contributions where Ee ' 1/me a2 ∼ 1 eV, with a = 1/me α. In this case the optic
spectra is present in the visible or ultraviolet.
3. The vibrational part Evibr. = (n + 1/2)ω. Given that the molecule is maintained
p in equilibrium
by coulombic forces one has that V (a) ∼ (1/2)µω a ∼ α/a so ω ∼ α/µa and νvibr. /νe '
p
2 2 3
me /mN ∼ 1/40 so the absorption is in the infrared (8000-50.000 Å). The temperature needed
to excite the vibrational modes is around 400 o K.
4. Finally one has the rotational part: Erot. /Ee = νrot. /νe ' (1/M a2 )/(1/me a2 ) ' me /M ∼ 10−4 .
The absorption is in the far infrared and microwaves (λ ∼ 1 mm-1 cm).
5. Thus the complete spectra can be written symbolically as

1 l(l + 1)
E = Ee + n + ω0 + (4.60)
2 2I
6. An important historical note is brought by the book of Townsend p. 258:
(a) The ‘discovery’ of the Big Bag background radiation A. McKellar (A. Mckellar, Publs.
Dominion Astro. Obs. (Victoria BC) 7 251 (1941)).
(b) By observing light coming from the ζ ophiuchi star, crosing the an interestelar cloud.
(c) He observed the absorption spectra of the molecule CN around the line λ = 3974 Å.
(d) In particular he measured the transitions due to the rotation of the molecule to obtain
λrotat. = 2.64 mm,
(e) that was interpreted as the transition in the rotational spectra from l = 1 to l = 0
(f) when the molecule is immersed in a radiation with T = 2.3 o K!,

(g) no far from the value obtained by Penzias and Wilson in this historical discovery T = 2.7
o K.
molec. Ed [eV] ν0 [eV] a [Å] 1/2I [eV] molec. Ed [eV] ν0 [eV] a [Å] 1/2I [eV]
H+
2 2.65 0.285 1.06 3.69·10−3 CO 9.6 0.269 1.13 2.39·10−4
H2 4.48 0.545 0.74 7.54·10−3 LiH 2.5 0.174 1.6 9.31·10−4
HD 0.47 0.74 5.69·10−3 HCl35 4.43 0.371 1.28 1.31·10−3
D2 0.39 0.74 3.79·10−3 NaCl35 4.22 0.045 2.36 2.36·10−5
Li2 0.044 2.67 8.39·10−5 KCl35 0.035 2.79 1.43·10−5
N2 9.75 0.293 1.09 2.48·10−4 KBr79 0.029 2.94 9.1·10−6
O2 5.08 0.196 1.21 1.78·10−4 HBr79 0.329 1.41 1.06·10−3
Cl2 2.48 0.070 1.99 3.03·10−5 NO 5.3 0.236 1.15 2.11·10−4
Table 4: Rotovibrational parameters for several diatomic molecules. From Eisberg Table 12.1, p.
467 and Brasden Table 9.2 p. 393. The vibration frequency is ν0 and the dissociation energy is
Ed = Ee − ω0 /2.
1. In general Raman spectra is due to molecular rotation and vibration [5, atomic phys.].
2. Spectra of purely rotation transitions in very far infrared and short microwave: ∆E ∼ 10−2 −10−3
eV.
3. Raman effect change in the wavelength of light that occurs when a light beam is deflected by
molecules. The phenomenon is named for Sir Chandrasekhara Venkata Raman, who discovered
it in 1928.
4. When a beam of light traverses a dust-free, transparent sample of a chemical compound, a small
fraction of the light emerges in directions other than that of the incident incoming) beam.
5. Most of this scattered light is of unchanged wavelength. A small part, however, has wavelengths
different from that of the incident light; its presence is a result of the Raman effect.
6. Raman scattering is perhaps most easily understandable if the incident light is considered as con-
sisting of particles, or photons (with energy proportional to frequency), that strike the molecules
of the sample.
7. Most of the encounters are elastic, and the photons are scattered with unchanged energy and
frequency. On some occasions, however, the molecule takes up energy from or gives up energy to
the photons, which are thereby scattered with diminished or increased energy, hence with lower
or higher frequency.
8. The frequency shifts are thus measures of the amounts of energy involved in the transition
between initial and final states of the scattering molecule.
9. The Raman effect is feeble; for a liquid compound the intensity of the affected light may be only
1/100,000 of that incident beam.
10. The pattern of the Raman lines is characteristic of the particular molecular species, and its
intensity is proportional to the number of scattering molecules in the path of the light.
11. Thus, Raman spectra are used in qualitative and quantitative analysis.
12. The energies corresponding to the Raman frequency shifts are found to be the energies associated
with transitions between different rotational and vibrational states of the scattering molecule.
13. Pure rotational shifts are small and difficult to observe, except for those of simple gaseous
molecules.
14. In liquids, rotational motions are hindered, and discrete rotational Raman lines are not found.
15. Most Raman work is concerned with vibrational transitions, which give larger shifts observable
for gases, liquids, and solids.
16. Gases have low molecular concentration at ordinary pressures and therefore produce very faint
Raman effects; thus liquids and solids are more frequently studied.
4.3.2 Stern-Gerlach Experiment

1. Stern-Gerlach experiment (Stern-Gerlach 1922, Phipps and Taylor 1927 [4])).
2. For the case of Ag in the Stern-Gerlach the spin and the orbital momenta of the first 46 electrons
vanish as the orbital momenta of the 47-th one.
3. Thus the atomic angular momenta is the spin of the 47-th electron, that is 1/2.
4. For the Phipps and Taylor experiment H(l = 0), so Jatom. = se = 1/2, too. Thus in both
experiments two lines were obtained.
See Fig. 4 Magnet in Stern-Gerlach experiment A beam of silver atoms is passed between the...
Figure 2: The apparatus shown measures the x and y components of spin angular momentum...
F = ∇ (µ · B)
Fz = µ · (∇z B) (4.61)
demonstration of the restricted spatial orientation of atomic and subatomic particles with mag-
netic polarity, performed in the early 1920s by the German physicists Otto Stern and Walther
Gerlach.
5. In the experiment, a beam of neutral silver atoms was directed through a set of aligned slits,
then through a nonuniform (nonhomogeneous) magnetic field (see Figure 4), and onto a cold
glass plate.
6. An electrically neutral silver atom is actually an atomic magnet: the spin of an unpaired electron
causes the atom to have a north and south pole like a tiny compass needle.
7. In a uniform magnetic field, the atomic magnet, or magnetic dipole, only precesses as the atom
moves in the external magnetic field.
Figure 4.4: Stern-Gerlach experiment
8. In a nonuniform magnetic field, the forces on the two poles are not equal, and the silver atom
itself is deflected by a slight resultant force, the magnitude and direction of which vary in relation
to the orientation of the dipole in the nonuniform field (see Figure 2).
9. A beam of neutral silver atoms directed through the apparatus in the absence of the nonuniform
magnetic field produces a thin line, in the shape of the slit, on the plate.
10. When the nonuniform magnetic field is applied, the thin line splits lengthwise into two distinct
traces, corresponding to just two opposite orientations in space of the silver atoms.
11. If the silver atoms were oriented randomly in space, the trace on the plate would have broadened
into a wide area, corresponding to numerous different deflections of the silver atoms.
12. This restricted orientation, called space quantization, is manifested by other atoms and sub-
atomic particles that have nonzero spin (angular momentum), with its associated magnetic
polarity, whenever they are subjected to an appropriate nonuniform magnetic field. Landé’s
Factor.
4.3.3 Pauli Equation

The Schrodinger Equation obviously do not include spin. Around 1930 P. Dirac was able to find an
equation including in a consistent way the spin, Quantum Mechanics and Special Relativity for the
electron. This is the so called Dirac Equation the main equation in Relativistic Quantum Mechanics
[23]. It is incomplete because the fields (EM) are classical. The full theory, QED [23] takes into account
the quantum character of the fields and it is theoretically consistent with QM, Special Relativity, EM,
spin, etc. In the case of a non-relativistic electron a simpler equation can be used, is the Pauli’s
Equation [23]. In order to obtain it let’s begin by including EM (classical). This is done by the so
called ‘minimal substitution’ (p → p − qA, with q the electric charge and A the potential vector), or
by ’gauged’ the SE like in a Gauge Theory [25], given that for the electron q = −e
(p + eA)2 1
H = + V (r) = p2 + ep · A + eA · p + e2 A2 + V (r)
2m 2m
1 e
= p + 2eA · p + e2 A2 + V (r) ' H0 + A · p
2
(4.62)
2m m
Where the Coulomb or radiation gauge ∇ · A = 0 was chosen (remembering that one can do this
because the potential vector is unphysical, B = ∇ × A. In the last equation H0 = p2 /2m + V (r) is
the usual Hamiltonian and it was assumed that the potential vector is small as well as it is multiplied
by the electric charge. In general the last term describes correctly many atomic radiation phenomena
(see Radiation Chapter), but in this case we are going to consider only that atoms are affected by an
external magnetic field, constant. The corresponding potential, in the Coulomb gage is A = B × r/2
and
e e e
H = H0 + (B × r) · p = H0 + B · (r × p) = H0 + B · L = H0 − µL · B (4.63)
2m 2m 2m
with L = r × p the orbital angular momenta. The last term correspond to the energy of a magnetic
momenta µL = −(e/2m)L ≡ −µB L in presence of a constant magnetic field, H = −µ · B. Notice that
this is the classical (and quantum) magnetic momenta of an spinning electron.
It happens, however that the intrinsics magnetic momenta (µe = −ge µB Se ' −2µB Se = −eσ/2m)
of the electron is affected by the same magnetic field and its contribution is of the same order, so it
has to be included:
e
H = H0 + B · L − µe · B = H0 + µB L · B + ge µB S · B ' H0 + µB (L + 2S) · B (4.64)
2m
Having the Hamiltonian one can written the usual SE. Now, in this case the hamiltonian and
therefore the wavefuntion have two components.
The intrinsic magnetic momenta of the electron is given as µe = −ge µB Se ' −2µB Se = −eσ/2m
(Bransden AM 209), with µB = e~/2me = 5.8·10−5 eV/Tesla. Experimentally g/2 = 1.001 159 652 188 4(43)
(so we used g = 2)) [g − 2, 23]. Dirac eq. predicts g = 2 and QED ge = 2(1 + a) with a =
α/2π − 0.328(α/π)2 + · [g − 2, 23], the anomalous magnetic momenta of the electron [23, 25]. Similar
expresions are valid for atoms, and the other leptons with their correspondig g.
Similarly one has for the nuclei that µN = gN µN SN , with the nuclear magneton µN = e~/2mp =
3.15 · 10−8 eV/Tesla, gp ' 2 · 2.79278 and gn = 2 · (−1.91315). As theoretically one expects g = 2 for
a fundamental or structureless particle a measurement of g 6= 2 it is a clear indication of a composed
particle, like proton (Stern 30-s!), neutron, etc.
elementm, (Z, A) J P µ/µN Q τ

n, (0, 1) 1/2+ −1.91304273(45) 616.3 s
p, (1, 1) 1/2+ 2.792847351(28) stable
D, (1, 2) 1+ 0.8574382329(92) stable
T, (1, 3) 1/2+ 2.9789622487 0.00286015 12.33y
He, (2, 3) 1/2+ −2.127624857 stable
He, (2, 4) 0 0
(4.65)
Li, (3, 6) 1+ 0.82204736 stable
Li, (3, 7) 3/2− 3.256426817 −0.00083 stable
Be, (4, 9) 3/2− −1.17789 0.053 stable
B, (5, 8) 2+ 1.0355 0.77s
B, (5, 10) 3+ 1.8006448 0.08472 stable
C, (6, 12) 0 0
O, (8, 16) 0 0
Table 5: E. Cohen and B. Taylor, Rev. Mod. Phys. 59, 1121 (1987); P. Raghavan, et al. Nucl. Data
Tables 42, 189 (1989) [4]. See table 5.1 in Bransden AM 235.
4.3.4 Magnetic dipoles in magnetic fields

Let’s see the contribution to the energy eigenvalues due to a magnetic dipole moment in presence of
a magnetic field. The Hamiltonian in this case is
H = −µ · B (4.66)
As we saw the magnetic dipole momenta can be written in general as µ = gµB,N J, with g the
gyromagnetic ratio we mention before for the electron, proton and neutron. If the particle is an
electron or an atom we take for µB,N the Magneton of Bohr, while it is a nuclei we have to take the
Nuclear magneton we mention before. The Schrödinger equation can be solved easily if we chose the
z-axis along the magnetic field: H = −gµB,N BJz and the energy levels are
EJ,mJ = −gµB,N BmJ (4.67)
and the eigenfunctions are the vectors |JmJ >. The general solution is
X
ψ(t) = amJ e−iEmJ t |JmJ > (4.68)
mJ
with amJ arbitrary coefficients, that may be determinated by the initial configuration. Let’s see
the expectation values
X
E =< ψ|H|ψ >= |amJ |2 EmJ
mJ
X
< Jz >= |amJ |2 mJ
mJ
X p
< J± >= a∗mJ ±1 amJ e∓iωt J(J + 1) − mJ (mJ ± 1) ≡ ae∓iωt (4.69)
mJ
p
where ω = gµB,N B, and we have used J± |JmJ >=P∗ J(Jp+ 1) − m(m ± 1). Now one can write
< J± >= |a| exp(∓iωt − iφ) because |a| exp(−iφ) = mJ amJ J(J + 1) − mJ (mJ ± 1), so
< Jx >= |a| cos(ωt − φ) = |J| sin(θ) cos(ωt − φ)

< Jy >= −|a| sin(ωt − φ) = |J| sin(θ) sin(ωt − φ)
X
< Jz >= |amJ |2 mJ = |J| cos(θ) (4.70)
mJ
P
given that |J| cos(θ) ≡ mJ |amJ |2 mJ and |J| sin(θ) ≡ |a| That corresponds to the precession of
the magnetic momenta around B, with ω angular frequency (g = 1 means ω = ωLarmor = eB/2m and
we have the classical case). See Fig. 5. This is the basic principle of NMR: if you measure ω, the
precession frequency the you can get g for each particle and given that each molecule has a particular
value we can recognize what substance you have. The cyclotron frequency is ωC = eB/m. Cyclotron
frequency is the angular rotation frequency for a particle in presence of a Constant Magnetic Field
ωL = eB/m (Lorrain-Corson p. 287). The Larmor frequency is the precession frequency of a magnetic
dipole in presence of a Constant Magnetic Momenta τ = µ ∧ B so L̇ = µ ∧ B = gµB,N L ∧ B = L ∧ ω,
where ω = ωL = eB/2m (Landau II, p. 140 and Feynman 34-7) (see Merzbacher pag. 281 and Schiff
384. See Ehrenfest theorem: statistical mechanics, Spin precession in sakurai p. 161).
4.3.5 Paramagnetic Resonance

In this case the dipole is immersed in two fields: the usual static one and another due to the electro-
magnetic wave used to excite it (Gasiorowicz 237, Landau 502, Merzbacher 283). See Fig. 6

1 1 ω0 ω1 cos(ωt)
H = −µ · B = −gµB/N B · J = gµB/N B · σ = − (4.71)
2 2 ω1 cos(ωt) −ω0
with ω0 = gµB B0 and ω1 = gµB B1 . The Pauli/Scrödinger equation becomes

ϕ̇1 1 ω0 ω1 cos(ωt) ϕ1
i =− (4.72)
ϕ˙2 2 ω1 cos(ωt) −ω0 ϕ2
and taking ϕ1 = a exp[iω0 t/2] and ϕ2 = b exp[−iω0 t/2] one gets
2iȧ = −ω1 cos(ωt)e−iω0 t b, 2iḃ = −ω1 cos(ωt)eiω0 t a (4.73)

If = ω0 − ω << ω0 one has that (a more complete solution, from the mathematical point of view
can be founded in ref. [6])
1 i(ω±ω0 )t 1
cos(ωt)e±iω0 t = e + e−i(ω∓ω0 )t ' e∓it (4.74)
2 2
and
4iȧ = −ω1 eit b, 4iḃ = −ω1 e−it a (4.75)
if b is eliminated one obtains
ω 2
1
ä + iȧ + a=0 (4.76)
4
that can be solved by using the trial function a = a0 exp(iλt) and
q
1
λ = λ± = − ± + ω1 /4
2 2 (4.77)
2
taking a(0) = 1 and b(0) = 0 (so ȧ(0) = 0), then
1 h i 4λ− λ+ h i
a = −λ− eiλ+ t + λ+ eiλ− t , b = eiλ+ t − eiλ− t eit
λ+ − λ− ω1 (λ+ − λ− )

λ+ λ− i(λ+ −λ− )t iλ− −ω0 /2)t
ϕ1 = 1− e e
λ+ − λ− λ+
2λ− λ+ h i
ϕ2 = ei(λ+ −λ− )t − 1 eiλ− +ω0 /2+)t (4.78)
ω1 (λ+ − λ− )
so the probabilities are
" 2 #
λ+ 2 λ− λ − 1
P1 = 1+
−2 cos(λ+ − λ− )t → [1 + cos(ω1 t/2)]
λ+ − λ− λ+ λ+ 2
2
4λ− λ+
P2 = 2 [1 − cos(λ+ − λ− )t] → 1 [1 − cos(ω1 t/2)] (4.79)
λ+ − λ− 2
in the case of resonance when → 0. See Fig. 7.

4.3.6 NRM
1. Nuclear magnetic resonance abbreviated as NMR [6] selective absorption of very high-frequency
radio waves by certain atomic nuclei that are subjected to an appropriately strong stationary
magnetic field.
2. This phenomenon was first observed in 1946 by the physicists Felix Bloch and Edward M. Purcell
independently of each other.
3. Nuclei in which at least one proton or one neutron is unpaired act like tiny magnets, and a
strong magnetic field (B ' 0.2 − 2 T) exerts a force that causes them to precess in somewhat
the same way that the axes of spinning tops trace out cone-shaped surfaces while they precess
in the Earth’s gravitational field.
4. The nuclear spin, sN vanish if the number of protons np and the number of neutrons nn are
both even. If np + nn is odd sn = 1/2, 3/2, · · · . If np + nn is even sn = 1, 2, · · · (?).
5. When the natural frequency of the precessing nuclear magnets corresponds to the frequency of
a weak external radio wave striking the material, energy is absorbed from the radio wave.
6. This selective absorption, called resonance, may be produced either by tuning the natural fre-
quency of the nuclear magnets to that of a weak radio wave of fixed frequency or by tuning
the frequency of the weak radio wave to that of the nuclear magnets (determined by the strong
constant external magnetic field).
7. Nuclear magnetic resonance is used to measure nuclear magnetic moments, the characteristic
magnetic behavior of specific nuclei.
8. Because these values are significantly modified by the immediate chemical environment, however,
NMR measurements provide information about the molecular structure of various solids and
liquids.
9. Several nobel prized have been awarded by developments in this field.
(a) I. Rabi got his nobel prize in 1944 for ‘his resonance method for recording the magnetic
properties of atomic nuclei’
(b) N. Ramsey got the nobel prize in 1989 for been the first to measure a nuclear magnetic
dipole moment.
(c) F. Bloch and E. Purcell in 1952 for ‘their development of new methods for nuclear magnetic
precision measurements and discoveries in connection therewith’.
(d) They were the first to measures magnetic dipole moments of nuclei in bulk matter.
(e) R. Erns got its nobel prize in chemistry in 1991 for its work in NRM spectroscopy.
(f) Finally P. Lauterbur and P. Mansfield got the 2003 Nobel Medicine Prize for magnetic
resonance imaging method (MRI) [6].
10. By the early 1980s nuclear magnetic resonance techniques had begun to be used in medicine to
visualize soft tissues of the body.
Resr
umass
Figure 4.5: NRM

11. This application of NMR, called magnetic resonance imaging (MRI), presented a hazard-free,
noninvasive way to generate visual images of thin slices of the body by measuring the nuclear
magnetic moments of ordinary hydrogen nuclei in the body’s water and lipids (fats).
12. NMR images show great sensitivity in differentiating between normal tissues and diseased or
damaged ones.
13. By the late 1980s MRI had proved superior to most other imaging techniques in providing images
of the brain, heart, liver, kidneys, spleen, pancreas, breast, and other organs.
14. MRI provides relatively high-contrast, variable-toned images that can show tumors, blood-
starved tissues, and neural plaques resulting from multiple sclerosis.
15. The technique presents no known health hazards, but it cannot be used on individuals who have
cardiac pacemakers or certain other metal-containing devices implanted in their bodies.
4.3.7 Electron-Spin Resonance

1. Electron paramagnetic resonance (epr), also called ELECTRON-SPIN RESONANCE (esr), se-
lective absorption of weak radio-frequency electromagnetic radiation (in the microwave region)
by unpaired electrons in the atomic structure of certain materials that simultaneously are sub-
jected to a constant, strong magnetic field.
2. The unpaired electrons, because of their spin, behave like tiny magnets.
3. When materials containing such electrons are subjected to a strong stationary magnetic field,
the magnetic axes of the unpaired electrons, or elementary magnets, partially align themselves
with the strong external field, and they precess in the field much as the axes of spinning tops
often trace cone-shaped surfaces as they precess in the gravitational field of the Earth.
4. Resonance is the absorption of energy from the weak alternating magnetic field of the microwave
when its frequency corresponds to the natural frequency of precession of the elementary magnets.
5. When either the microwave frequency or the stationary field strength is varied and the other is
kept fixed, the measurement of radiation absorbed as a function of the changing variable gives
an electron paramagnetic resonance spectrum. Such a spectrum, typically a graph of microwave
energy absorption versus applied stationary magnetic field, is used to identify paramagnetic
substances and to investigate the nature of chemical bonds within molecules by identifying
unpaired electrons and their interaction with the immediate surroundings.
6. In contrast to nuclear magnetic resonance, electron-spin resonance (ESR) is observed only in a

restricted class of substances.
7. These substances include transition elements–that is, elements with unfilled inner electronic
shells–free radicals (molecular fragments), metals, and various paramagnetic defects and impu-
rity centers.
8. Another difference from NMR is a far greater sensitivity to environment; whereas the resonance
frequencies in NMR in general are shifted from those of bare nuclei by very small amounts
because of the influence of conduction electrons, chemical shifts, spin-spin couplings, and so on,
the ESR frequencies in bulk matter may differ greatly from those of free spins or free atoms
because the unfilled subshells of the atom are easily distorted by the interactions occurring in
bulk matter.
9. A model that has been highly successful for the description of magnetism in bulk matter is based
on the effect of the crystal lattice on the magnetic center under study. The effect of the crystal
field, particularly if it has little symmetry, is to reduce the magnetism caused by orbital motion.
To some extent the orbital magnetism is preserved against ligand fields of low symmetry by the
coupling of the spin and orbital momenta.
10. The total energy of the magnetic center consists of two parts: (1) the energy of coupling between
magnetic moments due to the electrons and the external magnetic field, and (2) the electrostatic
energy between the electronic shells and the ligand field, which is independent of the applied
magnetic field.
11. The energy levels give rise to a spectrum with many different resonance frequencies, the fine
structure. Another important feature of electron-spin resonance results from the interaction
of the electronic magnetization with the nuclear moment, causing each component of the fine-
structure resonance spectrum to be split further into many so-called hyperfine components.
12. If the electronic magnetization is spread over more than one atom, it can interact with more than
one nucleus; and, in the expression for hyperfine levels, the hyperfine coupling of the electrons
with a single nucleus must be replaced by the sum of the coupling with all the nuclei.
13. Each hyperfine line is then split further by the additional couplings into what is known as super-
hyperfine structure. The key problem in electron-spin resonance is, on one hand, to construct a
mathematical description of the total energy of the interaction in the ligand field plus the applied
magnetic field and, on the other hand, to deduce the parameters of the theoretical expression
from an analysis of the observed spectra.
14. The comparison of the two sets of values permits a detailed quantitative test of the microscopic
description of the structure of matter in the compounds studied by ESR.
15. The transition elements include the iron group, the lanthanide (or rare-earth) group, the palla-
dium group, the platinum group, and the actinide group.
16. The resonance behavior of compounds of these elements is conditioned by the relative strength
of the ligand field and the spin-orbit coupling.
17. In the lanthanides, for instance, the ligand field is weak and unable to uncouple the spin and
orbital momentum, leaving the latter largely unreduced.
18. On the other hand, in the iron group, the components of the ligand field are, as a rule, stronger
than the spin-orbit coupling, and the orbital momentum is strongly reduced.
19. The advent of ESR has marked a new understanding of these substances. Thus, it was formerly
thought that in the iron group and the lanthanide group ions of the crystal were bound together
solely by their electrostatic attraction, the magnetic electrons being completely localized on the
transition ion.
20. The discovery of superhyperfine structure demonstrated conclusively that some covalent bonding
to neighboring ions exists. With few exceptions, the magnetic moments of imperfections such
as vacancies at lattice sites and impurity centers in crystals that give rise to an observable ESR
have the characteristics of a free electronic spin. In the study of these centers, hyperfine and
superhyperfine structure provide a mapping of the electronic magnetization and make it possible
to test the correctness of the model chosen to describe the defect.
21. The most widely studied by resonance are those of phosphorus, arsenic, and antimony, substi-
tuted in the semiconductors silicon and germanium.
22. Studies of hyperfine and superhyperfine structure give detailed information on the status of these
impurities. Free radicals are ideally suited for study by electron-spin resonance. They can be
studied in a concentrated form or in very dilute solutions. The sensitivity of ESR is particularly
important for the study of very short-lived species.
23. The ESR of free radicals in solutions gives an extreme wealth of hyperfine lines because the
magnetic electron is not localized on one nucleus but interacts with several nuclei of the radical.
4.3.8 LS and JJ Schemes

LS : S. O. << H Russell-Saunders. Base |lml > |S, ms > JJ : S. O. >> H. Base |Jm; ls >
4.4. ANGULAR MOMENTA EXERCISES 127
4.4 Angular Momenta Exercises

4.4.1 Orbital Angular Momenta Exercises
1. Show
d
 = − < ∇V >=< F >
dt
d
< L > = − < r ∧ (∇V ) >=< τ > (4.80)
dt
A: Given that H = p2 /2m + V (x), [pi , V ] = −i (∇i V ) = iFi and [Li , p2 ] = 0 one obtains
d ∂
i = < [p, H] > +i =< [p, V ] >= i < F >
dt ∂t
d ∂ 1
i < Li > = < [Li , H] > +i < Li >= < [Li , p2 ] > + < [Li , V ] >= ijk < [xj pk , V ] >
dt ∂t 2m
= ijk < xj [pk , V ] >= iijk < xj (Fk ) >= i < τi > (4.81)
2. Show that [Li , xj ] = iijk xk , [Li , pj ] = iijk pk and [Li , Lj ] = iijk Lk .
3. Show that [Li , x2 ] = [Li , p2 ] = [L2 , xi ] = [L2 , pi ] = [Li , x · p] = [L2 , x · p] = 0.
4. Obtain px , py and pz in spherical coordinates. From that compute Li .

A: px = (∂r/∂x)pr + (∂θ/∂x)pθ + (∂φ/∂x)pφ
5. Show explicitly that [Li , f (r)] = [Li , f (p)] = [L2 , f (r)] = [L2 , f (p)] = 0 for an arbitrary
function f .
6. Show explicitly that [L± , Lz ] = ∓L± and [L+ , L− ] = 2Lz .
7. Obtain the eigenvalues of L2 is more complicated: one has to solve the equation

1 ∂2 1 ∂ ∂
L ψ=−
2
+ sin θ ψ = λψ (4.82)
sin2 θ ∂φ2 sin θ ∂θ ∂θ
Using the method of ‘Separation of variables’: ψ = Θ(θ)Φ(φ) = Θ(θ) exp[imφ]. In order to obtain
the same wavefunction after a rotation like φ → φ + 2π one obtains that m = 0, ±1, ±2, · · · .
The other equation is, then
∂ ∂ m2
(1 − ξ 2 ) Θ − Θ + λΘ = 0 (4.83)
∂ξ ∂ξ 1 − ξ2
with ξ = cos θ. In order to have finite solutions at ξ = ±1 lets try the solution Θ = (1 −
ξ 2 )m/2 h(ξ), with t = (1 − ξ)/2, 1 − t = (1 + ξ)/2 and
Θ0 = (1 − ξ 2 )m/2 h0 − mξ(1 − ξ 2 )m/2−1 h

Θ00 = (1 − ξ 2 )m/2 h00 − 2mξ(1 − ξ 2 )m/2−1 h0 − m(1 − ξ 2 )m/2−2 1 − (m − 1)ξ 2 h
(1 − ξ 2 )h00 − 2(m + 1)ξh0 + [λ − m(m + 1)] h = 0
t(1 − t)ḧ + (m + 1)(1 − 2t)ḣ + [λ − m(m + 1)] h = 0 (4.84)
and h = A2 F1 (a, b, c, t) (x(1 − x)2 F1 + [c − (a + b + 1)x] 2 F10 − ab2 F1 = 0), a√+ b + 1 =

2(m + 1), ab = √ m(m + 1) − λ, c = m + 1. The solutions are a = [2m + 1 ± 4λ + 1]/2,
b = [2m + 1 ∓ 4λ + 1]/2. In order to have a convergent series at ξ = ±1 one has that
a = −n = 0, −1, −2, · · · (a second solution is totally equivalent, given that F is symmetric
under the interchange of a and b) and
λ = (m + n)(m + n + 1) = l(l + 1), a ≡ m − l, l ≥ m + n, b = −n = m − l, n + 2m + 1 = l + m +(4.85)

1
The solution is the Associated Legendre polynomials:
Θ = Ā(1 − ξ 2 )m/2 2 F1 [m − l, l + m + 1, m + 1, (1 − ξ)/2] = APlm (ξ) (4.86)
given the boundary conditions (Θ has to be finite at ξ → ±1) one has that λ = l(l + 1).
8. Show the parity transformation for the Spherical Harmonics: Ylm (π − θ, φ + π) = (−1)l Ylm (θ, φ)
and that Yl,−m = (−1)m Ylm ∗ .
p
9. Show explicitly that L± Ylm = (l ∓ m)(l ± m + 1) Yl,m±1 , Lz Ylm = mYlm and L2 Ylm = l(l +
1)Ylm .
h i h i1/2 h i
(l−m)!
A: L± Ylm = e±iφ ± ∂θ ∂
+ i cot θ ∂φ∂
Ylm = 2l+1 (−1) m e±iφ ± ∂ + i cot θ ∂ eimφ P m (cos θ)
l
∂ m imφ 4π (l+m)! m
∂θ
∂φ
≡ Nlm e ±iφ ± ∂θh Pl + i cot θPl · im e
m
i= Nlm e
i(m±1)φ ∓ sin θP l − m sin θ Pl
0 cos θ m
√ m
= Nlm e i(m±1)φ ∓ 1 − x P l − √1−x2 Pl
2 0 mx m

= Nlm ei(m±1)φ (1/2) ∓Plm+1 ± (l + m)(l − m + 1)Plm−1 − Plm+1 + (l + m)(l − m + 1)Plm−1
p
= (l ∓ m)(l ± m + 1) Yl,m±1
10. For the case of angular momenta l = 1 (l = 2)find out the matrices Lx , Ly , L± , Lz y L2 . Show
explicitely how theypsatisfy the corresponding commutation relations.
p
A: Given L± Ylm = (l ∓ m)(l ± m + 1) Yl,m±1 (L± )lm,l0 m0 = (l ∓ m0 )(l ± m0 + 1) δll0 δm,m0 ±1 .
L− = L†+
 
0 2 √0 0 0
 
0 1 0  0 0 6 √0 0 
√  
for l = 1 L+ = 2 0 0 1 , for l = 2 L+ = 
 
 0 0 0 6 0 
 (4.87)
0 0 0  0 0 0 0 2 
0 0 0 0 0
11. Find out ∆Lx for the state |lm >.
12. Find ∆φ and ∆Lz , for an state of angular momenta l and z-component m. Comment what hap-
pens with the Heisenberg’s indetermination principle [1]. See PhysicsWeb, Angular uncertainty
passes test, oct.-04; S. Franke-Arnold, et al., New J. of Phys. 6, 103 (2004); S. Barnett and D.
Pegg, Phys. Rev. A 41, 3427 (1990).
13. Show that [H, Li ] = [H, L2 ] = 0 for any central potential, like the hydrogen case.
14. Show that the Schrödinder for a central potential can be written as −u00 = 2µ(E + Veff. (r))u (for
the radial part), where the Effective potential is Veff. (r) = V (r) + l(l + 1)/2µr2 and u = R/r.
15. An homogenous sphere of m = 100 grs. and r = 1 cm spins around its axis with a frequency of
1000 hz. Compute the value of l?
A: El = l(l + 1)~2 /2I = (1/2)Iω 2 = (1/2)I(2πν)2 → l ' 2πIν/~ = 4πmr2 ν/5~ = 4π · 0.1 ·
(10−2 )2 · 103 /5 · 10−34 ' 2.5 · 1032
16. Compute l for the earth?.

A:El = l(l + 1)~2 /2I = (1/2)Iω 2 = (1/2)I(2π/T )2 → l ' 2πI/~T = 4πmr2 ν/5~ = 4π · 5.98 ·
1024 (6.4 · 106 )2 · 103 kg · m2 /5 · 10−34 · 24 · 3600J · s = 7.1 · 1067 . ∆E ≡ El+1 − El = l~2 /I ' 5 · 10−39
J∼ 5 · 10−26 eV!.
17. What is the degeneracy of an sphere with l = 3?

A: Elm = l(l+1)~2 /2I. So there are 2l+1 = 7 states with the same energy: m = −3, −2, −1, 0, 1, 2, 3.
18. For an ellipsoid of revolution with l = 3 y |m| = 2 find the degeneration.

A: Elm = [l(l + 1) + (Ix /Iz − 1)m2 /2Ix . There are only two states with l = 3 y |m| = 2: |3, ±2 >,
given that the energy depends only on m2 .
4.4.2 Angular Momenta, general
19. Show eq. (4.16) in the general case.
20. Is it possible to find a particle with J = 0.3?, J = 2/3?, Jz = 0.7?
21. What are the irreducible representations of SU (2) (the angular group)?
22. What is the difference between spin and orbital angular momenta?
23. Suppose the electron spin were due to its rotation around its own axis. If it has been shown,
experimentally that the electron radius re < 10−19 mts, what is the minima speed of its surface
to produce the correct value for the spin?. Do the same for thr proton, assuming rp = 1 fm.
Notice that for the meutrino is even worst as its masss is very small.
A: Iω = (2mr2 /5)(v/r) = ~/2 so v/c = 5~c/4mr. For the electron v/c = 5 · 197.3 MeV · f/4 ·
0.5 · 10−4 MeV · f = 5 · 106 !. For the proton v/c = 5 · 197.3 MeV · f/4 · 938 MeV · f = 0.26
24. Show explicitly the Pauli matrices properties: a) [σi , σj ] = 2iijk σk , b) {σi , σj } = 2δij , c)
~ σ /2} = cos(φ/2) + i~n̂ · ~σ sin(φ/2) and e) obtain
(σ · A)(σ · B) = A · B + iσ · (A×B), d) exp{iφ·~
d (Rose 52). The Pauli’s matrices are
1/2

0 1 0 −i 1 0
σx = , σy = , σz =
1 0 i 0 0 −1
25. See neutron interferometry and the - sign in Sakurai p. 162-3
26. Obtain explicitly the eigenvalues and eigenvectors of the spin operator: s = (1/2)σ · n̂, given in
the eq. (4.36)).
27. Obtain for J = 1 the rotation matrix exp[iθ · J].

A:
     
1 0 1 1 0 −1 1 0 0
1 1
Jx2 =  0 2 0  , Jy2 =  0 2 0  , Jz2 =  0 0 0 
2 2
1 0 1 −1 0 1 0 0 1
and Ji3 = Ji
28. For J = 1 get for the spin operator, s = J · n̂, where n̂ is an arbitrary unitary vector the
eigenvalues and eigenvectors.
29. Work out the J = 3/2 and J = 2 cases. Check the obtained matrices satisfy all the commutation
relations.
30. Write out the matrices Jz and J 2 , in the case of J = 5/2.
31. Work out the d matrices giving the wavefunction transformation exp {iφ · J}, in the general case.
See Rose 52.
4.4.3 Sum of Angular Momenta
32. Show that: a) J = 12 σ and b) J = L + 12 σ satisfy the Angular Momenta commutation relations:
[Ji , Jj ] = iijk Jk . Show that the operators Jz , J 2 , L2 and σ 2 commute between themselves.
33. Show, in general that the operators Jz , J 2 , J12 and J2 commute between themselves, where
J = J1 + J2 .
34. Show that J1 · J2 , J1 · J and J2 · J are diagonal in the base |Jm; J1 J2 >. Obtain [J1z , J 2 ]
35. What is the value of J = 1 + 3/2 + 4?

36. Show, explicitly that J = 2 + 3/2 = 7/2, 5/2, 3/2, 1/2

5/2 (2, 1/2) J = 5/2 1 state
3/2 (1, 1/2) (2, −1/2) J = 5/2, 3/2 2 states
1/2 (0, 1/2) (1, −1/2) J = 5/2, 3/2 2 states
(4.88)
−1/2 (−1, 1/2) (0, −1/2) J = 5/2, 3/2 2 states
−3/2 (−2, 1/2) (−1, −1/2) J = 5/2, 3/2 2 states
−5/2 (−2, −1/2) J = 5/2 1 state
10 states 10 states
Table 6: J = 2 + 1/2. The total number of states is 10 = (2 · 2 + 1) · (2 · (1/2) + 1) =

(2 · (5/2) + 1) + (2 · (3/2) + 1).
m (m1 , m2 ) Base |J, m > Base Numb. of states

7 (5, 2) J =7 1 state
6 (4, 2), (5, 1) J = 7, 6 2 states
5 (3, 2), (4, 1), (5, 0) J = 7, 6, 5 3 states
4 (2, 2), (3, 1), (4, 0), (5, −1) J = 7, 6, 5, 4 4 states
3 (1, 2), (2, 1), (3, 0), (4, −1), (5, −2) J = 7, 6, 5, 4, 3 5 states
2 (0, 2), (1, 1), (2, 0), (3, −1), (4, −2) J = 7, 6, 5, 4, 3 5 states
1 (−1, 2), (0, 1), (1, 0), (2, −1), (3, −2) J = 7, 6, 5, 4, 3 5 states
0 (−2, 2), (−1, 1), (0, 0), (1, −1), (2, −2) J = 7, 6, 5, 4, 3 5 states (4.89)
−1 (−3, 2), (−2, 1), (−1, 0), (0, −1), (1, −2) J = 7, 6, 5, 4, 3 5 states
−2 (−4, 2), (−3, 1), (−2, 0), (−1, −1), (0, −2) J = 7, 6, 5, 4, 3 5 states
−3 (−5, 2), (−4, 1), (−3, 0), (−2, −1), (−1, −2) J = 7, 6, 5, 4, 3 5 states
−4 (−5, 1), (−4, 0), (−3, −1), (−2, −2) J = 7, 6, 5, 4 4 states
−5 (−5, 0), (−4, −1), (−3, −2) J = 7, 6, 5 3 states
−6 (−5, −1), (−4, −2) J = 7, 6 2 states
−7 (−5, −2) J =7 1 states
55 states 55 states
Table 7: J = 5 + 2. The total number of states is 55 = (2 · 5 + 1) · (2 · 2 + 1) = (2 · 7 + 1) + (2 ·

6 + 1) + (2 · 5 + 1) + (2 · 4 + 1) + +(2 · 3 + 1) = 15 + 13 + 11 + 9 + 7
37. For J = 2 + 3/2 obtain the states |j, m; j1 , j2 > in terms of the states |j1 , m1 > |j2 , m2 > and
the seconds in terms of the first ones.
38. For the case J = 1 + 3/2. a) What are the possible values of J?, b) Get |3/2, 1/2;J1 = 1,
J2 = 3/2 >, c) Get |1, 0; J1 = 1, J2 = 3/2 > and d) Get |1, 1 > |3/2, −1/2 >.
39. What are the possible values of J~1 · J~2 , J~1 · ~J and J~2 · ~J .
4.4.4 Applications
Raman Spectroscopy
40. Shortly, what is the Raman spectra and what are the typical wavelengths an frequencies involved.
41. Estimate the frequency emitted when a hydrogen molecule (H2 , B = 1/2I = 7.54 · 10−3 eV)
decays to the ground state of the rotational spectra. The temperature needed to see it. ∆E =
~2 /2I = ~ω so ν = ~/8πmp r2 ∼ 2 · 1011 hz. T = 4π~ν/kB p∼ 19 K. I1 = 2m11
o
p ra ' 3.3 · 10
2 −47
Kg·m , I2 = (8/5)me ra ' 1.5 · 10

2 2 −50 Kg·m ν
2 rot. ∼ (1/2π) 2~ν/mp ra ∼ 2 · 10 hz.
2
42. For a gas constituted of monatomic molecules at temperature T obtain the average energy?.
P P R 2 R 2
A: < E >= [ l e−l(l+1)/2IkB T l(l+1)/2I]/[ l e−l(l+1)/2IkB T ] ' [ dle−l /2IkB T l2 /2I]/[ dle−l /2IkB T ]
R 2 p
= −αkB T · [log dle−αl ]0 = −αkB T [log(1/2) π/α]0 = kB T
Pauli Equation
43. For the hydrogen atom, considering the electron spin find: a) the complete wavefunction for
the states 2s and 2p, b) the same for the states 3s and 3p, c) given that the strongest line of
hydrogen is the line Hα (produced by the transition from n = 3 to n = 2), how many line are
really present in the Hα -line?.
A: For the case of the hydrogen atom the wave function, considering the spin is Pψnlml sms =
Rnl Ylml χsms (work out the cases n=1,2). A more convenient basis is ψnJmJ ls = Rnl ml ms Ylm χsms .
44. For the hydrogen atom, considering the electron and proton spin find: a) the complete wave-
function for the states 1s and 2p, b) how many lines are really present in this transition?.
45. For the ‘spin-spin’ interaction, H 0 = As1 · s2 show that the solution can be written as ψ =
ψ(x)χs1 χs2 . Find out their energy eigenvalues.
A: Given that J = s1 + s2 one obtains that s1 · s2 = (JP
2 − J 2 − J 2 )/2 so ∆E = A[J(J + 1) −
1 J
J1 (J1 + 1) − J2 (J2 + 1)]/2 and ψ = ψ(x)χJmJ == ψ(x) m1 m2 CsJm m
J
,s
1 1 2 2 m χs 1 χs 2
m 1 m2
46. Show that the Semiclassical Theory of Radiation is a Gauge Theory: it is invariant under the
transformation, for all function α(x)
ψ → exp[iα(x)]ψ, qA → qA + ∇α (4.90)
Magnetic Moments in magnetic fields
47. A paramagnetic media (Reif 261) has temperature T and it is immersed in an external magnetic
field B. If its molecules have magnetic momenta µ what is their average energy?.
A:
" l
#
X X ∂ X
<E> = [ (−gµB mB)e−gµB mB/kB T ]/[ e−gµB mB/kB T ] = kB T β log e−mβ
m m
∂β
m=−l
l
X 2l
X
1−x x(2l+1)/2 − x−(2l+1)/2
2l+1 sinh[(2l + 1)β/2]
xm = x−l xk = x−l = =
1−x 1/2
x −x −1/2 sinh[β/2]
m=−l k=0

∂ sinh[(2l + 1)β/2] gµB B 2l + 1 β
< E > = kB T β log = (2l + 1) coth β − coth
∂β sinh[β/2] 2 2 2

1 2l + 1 β
< m > = − (2l + 1) coth β − coth
2 2 2
1 (gµB B) 2
<E> → l(l + 1) (4.91)
3 kB T
with β = gµB B/kB T , x = exp[−β], and given that coth x ' x + x/3 + · · · . The last limit is the
Curie’s law, Reif 214 valid when T → ∞.
48. What is the typical energy splitting produced in a atom by the earth magnetic field?
A: E = −gµB Bm ∼ 1 · (5.8 · 10−5 eV /T ) · (5 · 10−5 T ) · 1 ∼ 3 · 10−9 eV, ν = E/2π~ ∼ 3 · 10−9 /2π ·
6.6 · 10−16 ∼ 0.7 MHz ' 700 Khz.
source B [T] ∆E [eV] ν [Mhz]

Interestelar 10−10
Earth surface 5 · 10−5 3 · 10−9 0.7
magnet 10−2 − 10−1
Sun 10−2
Large Magnet 2-30 10−3 2 · 105
Pulsed magnet 500-1000
Pulsar Magnetar 108−12
Nuclear surface 1012
Table 8: Pulsar magnetar, Record Gamma-Ray Flare Is Attributed to a Hypermagnetized Neutron

Star in Our Galaxy (Search & Discovery), Phys. Tod. may.-05
49. Show that (W. Louisell in [6])
ȧ1 = −iω1 a1 + iκe−i(ωt+φ a2

ȧ2 = −iω2 a2 − iκei(ωt+φ a1
h i
a1 (t) = e−iω1 t a10 cosh(κt) + ie−iφ a20 sinh κt
h i
a2 (t) = eiω2 t a20 cosh(κt) − ieiφ a10 sinh κt (4.92)
50. Commute the time needed by a magnetic dipole to radiate its energy.
A: P = (2/3)αω 4 µ2 , ∆E = µB so T = 1/αµ2 (µB)3 = m2e ~/α(µB)3 = 137·(106 )2 ·10−16 /(10−4·0.1 )3 s =
1011 s
51. What is Nuclear magnetic Resonance (NMR)?. Why is it important?, can we do it by using the
electron spin?
52. To what temperature is it necessary to heat a hydrogen gas in order to be able to observe the
NRM, if it is in presence of a earth magnetic field (B ∼ 0.5 Gauss)?
53. What is the most general motion of a magnetic dipole momenta in a Constant Magnetic Mo-
menta?, classically?, quantically?. What is the difference with the Stern-Gerlag experiment?
54. What are the ‘Cyclotron’ and the ‘Larmor’ frequencies?
55. What is the phenomena of electron paramagnetic Resonance (ESR), and its utility?.
56. What is parahydrogen?, orthohydrogen?, parapositronium?, orthopositronium?, etc.

Bibliography
4.5 Angular Momenta references

[1] Angular momentum.
M. Rose, Elementary theory of Angular Momentum, Dover 1995.
A. Edmonds, Angular Momentum in Quantum Mechanics, Princeton U. P. 1960.
K. Rao and V. Rasjeswari, Quantum Theory of Angular Momentum: Selected Topics, Springer-
Verlag 1993.
PhysicsWeb, Angular uncertainty passes test, oct.-04
S. Franke-Arnold, et al., New J. of Phys. 6, 103 (2004)
S. Barnett and D. Pegg, Phys. Rev. A 41, 3427 (1990).
[2] Lie Groups theory texts

B. Wybourne, Classical Groups for Physicists, Wiley 1974.
R. Slansky, Group theory for Unified Model Building, Phys. Rep. 79, 1 (1981).
R. Cahn, Semi-simple Lie Algebras and their representations, Benjamin/Cummings 1984.
H. Georgi, Lie Algebras in Particle Physics (Lie Algebras in Particle Physics), Perseus 1999.
P. Carruthers, Spin and Isospin in Particle Physics, Gordon and Breach 1971.
R. Gilmore, Lie groups, Lie algebras and some of their applications, Wiley 1974.
N. Jacobson, Lie Algebras, Wiley 1962.
J. Humphreys, Introduction to Lie Algebras and Representation Theory, Springer 1972.
H. Samelson, Notes on Lie Algebras, Van Nostrand-Reinhardt 1969.
W. Mckay, J. Patera and D. Sankoff, Computers in Non Associative Rings and Algebras, ed. by
R. Beck and B. Kolman, Academic Press 1977.
[3] Spin
G. Uhlenbeck and S. Goudsmit, Naturw., 13, 953 (1925); Nature 117, 264 (1926). Eisberg, p.
300 in ref. [2]
Phys. Tod. Jun.-76, p. 40.
S. Tomonaga, The Story of Spin, U. Chicago Press 1997.
R. Clark and B. Wadsworth, A new spin on nuclei, Phys. World, Jul.-98, pag. 25 (1998).
K. Rith and A. Schäfer, The mystery of Nucleon Spin, Scie. Amer. Jul.-99, pag. 42 (1999).
K. von Meyenn and E. Schucking, Wolfang Pauli, Phys. Tod. Feb.-01, 43 (2001).
[4] Stern-Gerlach experiment.

O. Stern, Z. Phys. 7, 18 (1921).
W. Gerlach and O. Stern, Z. Phys. 8, 110 (1922); 9, 349 (1922); 9, 353 (1924); Ann. Phys. 74,
45 (1924).
135
136 BIBLIOGRAPHY
T. Phipps and J. Taylor, Phys. Rev. 29, 309 (1927). H (l=0), two lines.
B. Friedrich and D. Herschbach, Stern and Gerlach: How a Bad Cigar Helped Reorient Atomic
Physics, Phys. Tod. Dec.-03 53.
R. Frisch and O. Stern, Z. Phys. 85, 4 (1933). µp First time
I. Esterman and O. Stern, Z. Phys. 85, 17 (1933). µp First time
J. Kellogg, I. Rabi, and J. Zacharias, Phys. Rev. 50, 472(1936). µp First time. NRM method.
L. Young Phys. Rev. 52, 138 (1937). Review at that time.
[5] Raman spectroscopy

J. Ferraro, C. Brown, Kazuo Nakamoto, Kaszuo Nakamoto, Introductory Raman Spectroscopy,
Academic Press 2002.
W. Kroto, Molecular Rotations Spectra, Dover 2003. Chemistry Nobel 1996. Fulleres.
[6] NMR.
N. Ramsey, Early magnetic resonance experiments: roots and offshoots, Phys. Tod. Oct.-93, pag.
40.
G. Pake, NMR in bulk matter, Phys. Tod. oct.-93, 40; Sci. Amer., Magnetic Resonance, Aug.-
58, pag. 58.
J. Kellogg, I. Rabi, N. Ramsey and J. Zacharias, Phys. Rev. 56, 728 (1939).
A. French and E. Taylor, An Introduction to Quantum Physics, W. Norton 1978. p. 492
J. Rigden, Isaac Rabi: walking the path of God., Phys. World, nov.-99.
C. Guillou and F. Reniero, Magnetic Resonance sniffs out bad wine, Phys. World, Nov.-98,
pag.22.
R. Macomber, A complete introduction to modern NMR spectroscopy, Wiley 1998.
P. Hore, NMR: the toolkit, Oxford 2000.
B. Schwarzschild, Lauterbur and Mansfield awarded Nobel Medicine Prize for magnetic resonance
imaging, Phys. Tod. Dec.-03, 24.
J. Weil, J Bolton and J. Wertz, Electron Paramagnetic Resonance : Elementary Theory and
Practical Applications, Wiley 1994.
W. Louisell, A. Yariv and A. Siegman, Phys. Rev. 124, 1646 (1961). Sol. Para-equ.
A. Lande, Phys. Rev. 46, 477 (1934).
Chapter 5
Theory of Perturbations
In general analytical solutions can be obtained in very few situations. This is the case in Classical,
Quantum Physics or in any real situation case. Thus the equations describing (modelling) a real
situation are very complicate. It is fortunate that in many cases (but not in all, like in Strong
Interactions) an approximate solution is available. Of course this solution can be improved when more
and more corrections (perturbations) are taken into account.
Let us mention few examples:
1. The earth orbit is said to be an ellipse and it is in a very good approximation. It can be
obtained from the Newton Gravitational law between the sun and the earth. However this is
only an approximation!. In general one has many bodies in the solar system and the problem
can be very complicated. Fortunately the other contributions (Moon, Jupiter, Venus, finite size
of the sun, etc) happen to be small perturbations that correct the first approximation!, and even
they can be ignored in many situations!.
2. In the experiment of Rutherford it is assumed that α particles are scattered by the nucleus, by
a Coulomb force. Of course this is only a first approximation. Additional effects are the motion
of the α particle and the nucleus (the Coulomb potential is valid for static charges!), relativistic
effects, quantum effects (in NR QM one obtains the same Rutherford cross section!, but this is
again a first approximation), magnetic fields, etc.
3. For hydrogenic atoms again one take the Coulomb potential and find an analytical solution. Once
more this may be a good approximation (depending on the available accuracy) but many cor-
rections are present: relativistic, electron and neutron magnetic momenta, Quantum corrections
to the Coulomb potential an so on.
Of course many more example can be mentioned. This nice fact of nature is profited by perturba-
tion theory and is the main topic of this chapter. In other cases analytical solution are not available
but approximate solutions can be obtained. This is the second topic of this chapter.
5.1 Time independent perturbations (Rayleigh-Schrödinger)

5.1.1 No degenerate case
Suppose H = H0 + H 0 with |H 0 | << |H0 | in a sense that can be precised later. Suppose that one can
solve the unperturbed hamiltonian:
137
138 CHAPTER 5. THEORY OF PERTURBATIONS
Figure 5.1: Figures for the Perturbation theory

5.1. TIME INDEPENDENT PERTURBATIONS (RAYLEIGH-SCHRÖDINGER) 139
H0 ψn(0) = En(0) ψn(0) (5.1)
and of course one wish to solve the complete problem: Hψn = En ψn . If the perturbation is not
very large (H 0 << H0 , see Fig. 1) one has that
X
ψn = (0)
Cnm ψm (5.2)
m
Once this is replaced in the complete equation it is obtained that
X X
Cnm H 0 ψm
(0)
= (En − Em
(0)
)Cnm ψm
(0)
(5.3)
m m
(0) ∗
now one can multiply by ψl and integrate over all the space to get the eigenvalue equation
X (0)
X (0)
0 0
[Hlm − (En − El )δml ]Cnm = 0 or Hlm Cnm = (En − El )Cnl (5.4)
m m
R
0 =
with Hnl dV ψn∗ H 0 ψl . In order to solve it, for a weak perturbation an iterative solution can be
obtained. Both the energy and the constants can be expanded in powers of H 0
C = C (0) + C (1) + C (2) + · · ·

E = E (0) + E (1) + E (2) + · · · (5.5)
Replacing in eq. (5.4) and taking the zero-th order terms
(0)
0 = (En(0) − El )Cnl (0) (5.6)
and the solution, once the wavefunction is normalized at this order is Cln (0) = δnl . At first order
the equation obtained from (5.4) is
X (0) (1) (0)

0
Hlm (0)
Cnm = (En(0) − El )Cnl + En(1) Cnl (5.7)
m
if l = n then
0
En(1) = Hnn (5.8)
and if l 6= n
0
Hln
(1)
Cnl = (0) (0)
for l 6= n
En − El
(1)
Cnl = 0 for l = n (5.9)
where the last result was obtained from the normalization condition for the wavefunction at this
order. At second order
X (0) (2) (1) (0)

0
Hlm (1)
Cnm = (En(0) − El )Cnl + En(1) Cnl + En(2) Cnl (5.10)
m
If l = n then one can get
X 0 |2
|Hnm
En(2) = (0) (0)
(5.11)
m6=n En − Em
For l 6= n one can obtain
 
(2) 1 X H0 H0 Hnn0 H0
 nm lm nl 
Cnl = (0) (0) (0) (0)
− (0) (0)
(5.12)
En − El m6=n En − Em En − El
and again to have the wavefunction normalized to this order (see Sakurai, for Rayleigh)
1X 0 |2
|Hln
(2)
Cnn =− (5.13)
2 (0)
(En − E )2
(0)
l6=n l
5.1.2 Degenerate case

In this case one has to do the same eq. (5.6) but care has to be taken in order to account for the
(0)
possible degeneracy. In this case if l, n ∈
/ same label then Cnl = 0 and if l, n ∈ the same level then
(0)
the Cnl are undeterminate.
To first order the obtained relation is
X (0) (1) (0)

(0) 0
Cnm Hlm = (En(0) − El )Cnl + En(1) Cnl (5.14)
m
That in the case l, n ∈ the same level
X
0
Hlm − δlm En(1) Cnm
(0)
=0 (5.15)
m
This equation determinates completely the wavefunction to zeroth order and the energy spectra
to first order. Notice that for each level a set of equations (corresponding to its degeneracy) have to
(0)
be solved. In the case l, n ∈/ the same level (given that Cnl = 0 in this case)
X (0) (1) (1) 1 − δnl X

(0) 0 0
Cnm Hlm = (En(0) − El )Cnl , Cnl = (0) (0)
Hlm (0)
Cnm (5.16)
m En − El m∈n
(1)
Naturally Cnl = 0 when l, n ∈ the same label remains undeterminate. As before the normalization
condition forces them to vanish.
5.2. TIME DEPENDENT PERTURBATION THEORY 141
5.2 Time dependent Perturbation Theory

In the case the Hamiltonian can be written as H = H0 + H 0 (t), with H0 a time independent opera-
tors with eigenvalues and eigenvectors: Hψn = En ψn . The time dependent perturbation is described
by H 0 (t). The system now has to satisfy the time dependent SE: ı∂ψ/∂t = Hψ. For ‘small’ time
dependent perturbations the full wavefunction can be expanded in terms of the unperturbated eigen-
functions:
X
ψ(t) = cm (t)e−iEm t ψm (x)
m
X
0
iċn (t) = eiωnm Hnm cm (5.17)
m
where the last equation was obtained by replacing the first in the timeR dependent SE and projecting
into the n-state. The matrix element of H 0 is defined as Hnm 0 (t) = ψn∗ H 0 (t)ψm d3 x and ωnm =
En − Em . In the case the perturbation is ‘small’ one can solve for the coefficients c in powers of H 0 :
(0) (1) (2) (0)
cn = cn + cn + cn + · · · . At order zero the coefficients are constant: ċn = 0 and if initially the
(0)
system was in the state n0 one has that cn = δnn0 . At this order the perturbation obviously doesn’t
have any effect. At first order one obtains
X
0
n (t) =
iċ(1) eiωnm Hnm c(0)
m
m
Z t
cn (t) = δnn0 − i 0
dt e−iωnn0 t Hnn0
+ ··· (5.18)
0
The process can be continued to higher orders. In this case energy is not conserved: in order to
perturb the system one has to add or extract energy.
5.3 Interaction Picture

The time evolution of the states is controlled by the Hamiltonian, in the Schrödinger representation:
Z
∂
i |ψ(t) >S = H|ψ(t) >S , |ψ(t) >S = e−iHt |ψ(t = 0) >S , H = d3 xH (5.19)
∂t
In the Interactive picture the hamiltonian is splitted as H = H0 + HI , and the states are redefined
so their time evolution is controlled by HI , the interaction part:
∂
|ψ(t) >S ≡ e−iH0 t |ψ(t) >I , i |ψ(t) >I = HI |ψ(t) >I (5.20)
∂t
The solution to this SE can be written like |ψ(t) >I = U (t, t0 )|ψ(t0 ) >I with
∂
i U (t, t0 ) = HI U (t, t0 ) (5.21)
∂t
and the initial condition U (t0 , t0 ) = 1. This SE has an iterative solution of the form
Z t
U (t, t0 ) = 1 − i dt0 HI (t0 )U (t0 , t0 )
t0
Z t Z t Z t1
U (t, t0 ) = 1 − i dt1 HI (t1 ) + (−i) 2
dt1 HI (t2 ) dt2 HI (t2 ) + · · · (5.22)
t0 t0 t0
The integrals can be rearranged by using the identities like
Z Z Z Z
t t1
1 t t
dt1 HI (t1 ) dt2 HI (t2 ) = dt1 dt2 T [HI (t1 )HI (t2 )]
t0 t0 2! t0 t0
Z t Z t1 Z Z Z Z
t2
1 t t t
dt1 HI (t1 ) dt2 HI (t2 ) dt3 HI (t3 ) = dt1 dt2 dt2 T [HI (t1 )HI (t2 )HI (t3(5.23)
)]
t0 t0 t0 3! t0 t0 t0
where T means the time ordered product. Thus the complete solution can be written as
Z t Z
U (t, t0 ) = T exp −i dt0 HI (t0 ) , S ≡ lim U (t, t0 ) = T exp d4 xLI (x) (5.24)
t0 t,t0 →±∞
5.4 Semiclassical Aproximation (WKB Method)

The WKB (From Wetzel, Kramers and Brillouin who introduced these techniques to QM) method
is equivalent to the semiclassical approximation. In Optics is the Eikonal equation, or the Fermat’s
principle (Landau II, 172 and Born and Wolf, Principles of Optics, 110). In this approximation one
considers expansions in powers of S/~, to do that one replace ψ = exp[iS/~] in the SE:
~2 2 p2 (x)
− ∇ ψ + V ψ = Eψ, ∇2 ψ = − 2 ψ (5.25)
2m ~
where p2 (x) ≡ 2m(E − V (x)). Given that ∇ψ = (i∇S/~) exp[iS/~] and ∇2 ψ = [i∇2 S/~ −
(∇S/~)2 ] exp[iS/~],
(∇S)2 − i~∇2 S = p2 = 2m(E − V ) (5.26)
and expanding in powers of 1/~: S = S0 + (~/i)S1 + (~/i)2 S2 + · · · and to second order

(∇S0 )2 − 2i~(∇S0 ) · (∇S1 ) − ~2 (∇S1 )2 + 2(∇S0 ) · (∇S2 ) − i~ ∇2 S0 − i~∇2 S1 = p2 (5.27)
1) To order zero one obtains the Hamilton equation for the Action (the Classical Mechanics) :
(∇S0 )2 = p2 so
Z Z p
S0 = ± pdx = ± 2m(E − V )dx (5.28)
5.4. SEMICLASSICAL APROXIMATION (WKB METHOD) 143
2) At first order the equation is 2(∇S0 ) · (∇S1 ) + ∇2 S0 = 0 so in 1-D S10 = −p0 /2p and
1
S1 = − ln(p/p0 ) (5.29)
2
3) and finally to second order (∇S1 )2 + 2(∇S0 ) · (∇S2 ) + ∇2 S1 = 0 and (see Landau 186 in [1])
" #
1 p0 2 1 p0 0
S20 = ∓ −
4 2p3 p p
" Z 02 # Z
1 p0 p m F m F2
S2 = ± + dx = ± + dx (5.30)
4 p2 2p3 4 p3 2 p5
Given that (p0 /p2 )0 = [(1/p)(p0 /p)]0 = (1/p)(p0 /p)0 −(p0 )2 /p3 one can solve for (p0 /p)0 /p = (p0 /p2 )0 +
(p0 )2 /p3 and using the fact that p0 = mF/p, with F = −V 0 .
Example: α-Decay
The α-decay of a nuclei is (A, Z) → (A − 4, Z − 2) + α, with α = (A = 4, Z = 2) is a α-particle or
Helium nuclei (see Fig. 2). This simple theoretical treatment [15] was given by Gamow, Condon and
Gurney in 1928. Weisskopf
R 568, R p
Given that S0 = ± pdx = ±i kdx, with k = 2µ(V − E), one has at zero-th order
Z x
ψ = exp[iS0 /~] = exp − kdx (5.31)
0
the ± signs are for decay and absorbtion, respectively. Now
Z b
ψ(b) P (b) ψ(b) 2
= exp − kdx , so = = exp [−I] (5.32)
ψ(a) a P (a) ψ(a)
Rb
with I = 2 a kdx. Now V = (1/4π0 )[(Z − 2) · 2e2 /r] = 2(Z − 2)α/r (see Fig. 3) and E = V (b) =
2(Z − 2)α/b ≡ [2(Z − 2)α/a]c or c ≡ a/b = E/[2(Z − 2)(α/a)]. The integral is then (see Fig. 4)
Z tan−1 √1/c−1

p Z bp p
I = 2µE · 2 b/r − 1dr = 2 2µE · (2b) sin2 (θ)dθ
p ha p p i0
−1
= 2 2µEb tan
2 1/c − 1 − c(1 − c) (5.33)
where tan2 (θ) ≡ b/r − 1 (r = b cos2 (θ)). The Reduced mass µ = 4(A − 4)mp /A and
q h p p i
I = 8(Z − 2)α 2(A − 4)mp /AE · tan−1 1/c − 1 − c(1 − c) (5.34)
with a = (A − 4)1/3 · 1.4 · 10−15 mts. The collision frequency is v/2a, where v is the average speed
inside the nuclei and 2a is its diameter. The frequency of emission is equal to the collision frequency
time the probability of going out (exp[−I]), so the lifetime is
τ1/2 = (2a/v) exp[I] (5.35)
Taking v ' c/10 and α−1 = 137.04 and mp = 938.2 MeV on get for the 230 Th90 (Eα = 4.82 MeV)
that 2(Z − 2)α/a = 29.8 MeV, c = 0.1617 and I = 100.47 · 0.789 = 79.24 and T1/2 = 1.35 · 1013 seg =
Exp.
4.4 · 105 years, to be compared withe the experimental value T1/2 = 8 · 104 years. Another case is the
232 Th
90 (Eα = 4.12 MeV) that 2(Z − 2)α/a = 29.7 MeV, c = 0.139 and I = 108.68 · 0.84 = 91.67 and
Exp.
T1/2 = 3.45 · 1018 seg = 1.1 · 1011 years, to be compared withe the experimental value T1/2 = 1.4 · 1010
years.
One can obtain the relation
Z −2
ln T1/2 = α + β √ (5.36)
E
with α and β constants. This is the so called Geiger-Nuttal law (1911-2). See N. Ashby and S.
Miller, principles of Modern Physics, p. 447; Gasiorowicz in ref. [1, 15], pgs. 90-92 and fig. 5-13; Park
3-D problem and Schiff p. 271 (range of validness). See Weisskopt 578, table 3.2; Cottingham p. 82
table 6.1. Park 451.
5.4.1 Bohr-Sommerfeld Quantization rules

Semiclassical approximation is not valid at the return points where the momenta vanish p = 0. At
these points points the SE has to be solved, without employing this approximation. Far from these
points (see Fig. 5) the wavefunction can be approximated as
Z x Z x
C1 C3
ψI (x) = √ exp q dx , ψIII (x) = √ exp − q dx
q a q b
Z x Z x
C2 C20
ψII (x) = √ exp i k dx + √ exp −i k dx (5.37)
q a q a
with q 2 = 2m(V − E) ≥ 0, k 2 = 2m(E − V ) ≥ 0 and unknown constants have to be determinated

by the boundary and normalization conditions. In order to complete the solution one has to solve the
SE at the return points a and b. For x ∼ a the potential can be expanded as V (x) = E −F (x−a)+· · · ,
with F = −V 0 (x = a) ≥ 0. Replacing in the SE, for x ∼ a
ψ 00 − 2mF (a − x)ψ = 0, ψ 00 − ξψ = 0 (5.38)
where in order to obtain the second form of the SE ξ ≡ α1/3 (a − x) with α = 2mF . The solution
is the the Airy function Φ(ξ) [5]. Thus the solution for x ∼ a is
5.4. SEMICLASSICAL APROXIMATION (WKB METHOD) 145
Figure 5.2: Geiger-Nuttal law

(
0 [1/2ξ 1/4 ] exp[−2ξ 3/2 /3]
0 if ξ → ∞
ψ(x) = A Φ(ξ) → A
[1/|ξ| ] sin[2|ξ| /3 + π/4] if ξ → −∞
1/4 3/2
( √ Rx
[1/2 q] exp[− a q dx] if x → −∞
→ A √ Rx (5.39)
[1/ k] sin[ a k dx + π/4] if x → ∞
given that q 2 = 2mF (a − x) = α2/3 ξ, k 2 = 2mF (x − a) = α2/3 |ξ| and
Z Z
a
2 x
2
q dx = ξ 3/2 , k dx = |ξ|3/2 (5.40)
x 3 a 3
At the other return point x ∼ b the potential is again expanded V (x) = E + F 0 (x − b) + · · · , with
F 0 = V 0 (x = b) ≥ 0. Replacing in the SE, for x ∼ b
ψ 00 − 2mF 0 (x − b)ψ = 0, ψ 00 − ηψ = 0 (5.41)

with η ≡ β 1/3 (x − b) and β = 2mF 0 . Again the solution for x ∼ b is
(
0 [1/2η 1/4 ] exp[−2η 3/2 /3]
0 if η → ∞
ψ(x) = B Φ(η) → B
[1/|η| ] sin[2|η| /3 + π/4] if η → −∞
1/4 3/2
( √ Rx
[1/2 q] exp[− b q dx] if x → ∞
→ B √ Rb (5.42)
[1/ k] sin[ x k dx + π/4] if x → −∞
given that q 2 = 2mF 0 (x − b) = β 2/3 η, k 2 = 2mF 0 (b − x) = β 2/3 |η| and
Z Z
x
2 b
2
q dx = η 3/2 , k dx = |η|3/2 (5.43)
b 3 x 3
One can see how these solutions have the same form of the semiclassical expansion: one can mach
the semiclassical solutions by choosing properly the constants c. Furthermore the two solutions, at
x = a and b have to be the same in the region II!, so
Z x Z b
A B
ψII (x) = √ sin k dx + π/4 = √ sin k dx + π/4 (5.44)
k a k x
for all a < x < b. In order to do that one has to rewrite the second expression
Z b Z x Z x Z b
sin k dx + π/4 = sin − k dx + k dx + k dx + π/4
x a a x
Z x Z b
= − sin k dx − k dx − π/4
a a
Z b
A sin [φ(x)] = −B sin φ(x) − k dx − π/2
a
Z x
φ(x) ≡ k dx + π/4 (5.45)
a
5.5. VARIATIONAL PRINCIPLE 147
and given that sin φ = (−1)n sin (φ ± nπ) and A = ±B one can conclude the quantization rules of
Bohr-Sommerfeld:
Z b Z bp
p dx = 2m[E − V (x)] dx = (n + 1/2)π (5.46)
a a
where a and b are the return points: V (a) = V (b) = E, for a given energy.
5.5 Variational principle

The Variational Principle was first applied by Lord Rayleigh in 1873 in Acoustics. Later on the method
was improved by W. Ritz in 1908. The basics of it it is the fact that
< φ|H|φ >

E[ψ] = ≥ E0 ∀φ (5.47)
< φ|φ >
where E0 is the energy of the ground state and φ is an arbitrary wavefunction satisfying the
boundary conditions. In order
P to show it one can decompose the wavefunction in terms of the unknown
eigenfunctions of H: φ = n an ψn . In this way one finds that
P
n | (En − E0 )
2
n |aP
E[φ] − E0 = ≥0 (5.48)
n |an |2
given that E0 is the ground state energy. In practice one has to make a guess of the function
φ based into previous experience. Normally the wavefunction is chosen with several (few) arbitrary
parameters, that are then chosen to minimize E[φ]. The guessed wavefunction is not totaly arbitrary
as it has to satisfy the boundary conditions, no nodes can be present for the ground state and it and
its derivative have to be continuous as usual. The method can be improved (see Pauling-Wilson 189
in [1] and [16]) to obtain an upper bound too, thus (E = E[φ] =< φ|H|φ > and D =< φ|H † H|φ >)
p p
E− D − E 2 ≤ Ek ≤ E + D − E 2 (5.49)
The method can be applied to exited states too. Assuming one has solved for N levels (knows E0 ,
E1 , · EN and ψ0 , ψ1 , · · · ψN as accurate as possible) and try to compute the next level (EN +1 and
ψN +1 ). Once again a trial function φ has to be choosen satisfiying the boundary conditions, orthogonal
to the lower energy wavefunctions (< φ|ψn > for n = 0, 1, · · · N ), constinuos as usual
P and with N nodes.
As before φ can be decomposed in terms of the unknown eigenfunctions: ψ = n>N an ψn and
P
n≥N +1 |an | (En
− EN +1 )
2
E[φ] − EN +1 = P 2
≥0 (5.50)
n≥N +1 |an |
and again E[φ] ≥ EN +1

5.6 Numerical Methods

5.6.1 Time independent 1D
Solving the time-independent Schr. Eq. in 1 dimension (radial or linear) (ordinary diff. eq.) Bound
State solutions
ψ(xi+1 ) = ψ(xi ) + ψ 0 (xi )∆x, ψ 0 (xi+1 ) = ψ 0 (xi ) + ψ 00 (xi )∆x

ψ 00 (xi ) = 2m[V (xi ) − E]ψ(xi ) (5.51)
In the ‘shooting’ method one starts the space evolution in one of the boundaries, pe. x = a with
the known value ψ(a) and a guess value for ψ 0 (a) and E. Evolves the solution until you reach the point
x = b. If you don’t obtain the boundary value of ψ(b) you have to change E and repeat the procedure
until you get the correct value for ψ(b) (see Fig. 6). Finally you have to normalize the solution. Some
help can be obtained ploting the value obtained for ψ(b) as a function of the energy when you evolve
the numerical solution. The ground state solution it is the one with no zeroes, the first exited stated
wave function has one zero, etc.
Semiclassical approximation (may be omitted) Applications: vibrations of bound H-Kr, electron
in a quantum well
5.6.2 Matrix diagonalization

In this case you have to guess a complete set of states as close as possible to the real solution, compute
the matrix Hij =< i|H|j > and diagonalize it (Landau-Paez 197, 231, momentum space). Naturally
its eigenvalues are the energy ones and the eigenvectors are the corresponding wave functions. Possible
basis are 1) discrete space, 2) the matrices x and p of (hermite polynomials), see Formalism chapter,
3) appropriate orthogonal polynomials (Hermite, Legendre, Laguerre, etc.), etc.
Solving Schroedinger Eq. in a basis: Matrix operations Comparison of Finite difference discrete
algorithms with matrix representations in a basis Variational properties Basis functions for atomic
calculations. (Gaussian, Slater) Calculations for molecules (and atoms) – Beyond this course to con-
struct general programs Calculations with Gaussian program ”Quantum Chemistry” package Iterative
methods General iterative methods for eigenvectors, related to time dependence
5.6.3 Time dependent

Solving the single-particle time-dependent Schr. Eq. (partial diff. eq.). Koonin 176. Unitary discrete
step methods that conserve energy 1-dimensional examples of evolution
”Computational Physics” by J. M. Thijssen, Cambridge Press, 1999. Available in paperback.
Zienkiewicz and Taylor, The Finite Element Method ,4th ed, McGraw-Hill,1989
J.-L. Liu, Computational Quantum Mechanics
A. Goswami, Quantum Mechanics, Wm. C. Brown Publisher, 1992
5.6.4 Scattering theory

Scattering from a spherical potential (Thijssen, Ch. 2; see also Koonin 87, Landau-Paez 239) Born
approximation Application: scattering of H from Kr
5.6. NUMERICAL METHODS 149
Scattering theory, phase shifts, and ab initio pseudopotentials Calculation of cross sections, trans-
port Eliminating core electrons to define pseudopotentials Modifying atomic program for pseudopo-
tentials (may be omitted)
5.6.5 Several particles

Hartree-Fock theory (Kooning 65) General variational theory for many particles Symmetry of the
wavefunction; Exchange for Fermions Koopman’s theorem Restricted/unrestricted theory applied to
atoms
”Hartree-Fock” theory for Bose condensates Recent interest in Bose condensates Reduces to self-
consistent equation in the Hartree approximation Hartree-Fock solution for atoms Working programs
for atoms Examples of solutions for ground and excited states Comparison of energies from Koopman’s
theorem and self-consistent solutions (”Delta H-F”)
Density Functional Theory
Juan Carlos Cuevas, Introduction to Density Functional Theory, Institut für Theoretische Festkörperphysik
Universität Karlsruhe (Germany) www-tfp.physik.uni-karlsruhe.de/c̃uevas
Functionals in quantum mechanics The Hohenberg-Kohn Theorem for many-body interacting sys-
tems Kohn-Sham approach for solving for ground state of a many-body interacting particle system as
a self-consistent problem of many-non-interacting particles
Methods for self-consistency Application to the atomic problem Modifying Hartree-Fock program
for Hartree-density-functional calculations Matching logarithmic derivative x=d (log psi)/dr for wave-
function Theorem relating dx/dE to integrated charge Algorithm for solving radial Schr. Eq.
The problem: basis sizes which grow as N! Prototype many-body problems Hubbard and Anderson
model for electrons Heisenberg model for spins The Lanczos method (exact diagonalization) for the
lowest states Applications to finite temperature statistical quantum mechanics (may be omitted)
5.6.6 Monte Carlos, Finite Temperature

The Lanczos method (exact diagonalization) for the lowest states Applications to finite temperature
statistical quantum mechanics (may be omitted) Monte Carlo methods (Koonin chp.8, Landau-Paez
93) High dimensional integration by statistical sampling Variational Monte Carlo with a trial corre-
lated wavefunction Slater-Jastrow two-body correlations Gutzwiller wavefunctions for the Hubbard
model Random walks, the Metropolis algorithm. Estimation of correlation and convergence Diffu-
sion Monte Carlo methods Exact solution of hydrogen molecule Comparison with Hartree-Fock, DFT
(using Gaussian program) Discussion of the ”sign problem” for Fermions Bose Condensates
M.H. Kalos and P.A. Whitlock, ”Monte Carlo Methods, Vol I”, Wiley, 1986. Probability, Sampling,
Tricks, Metropolis, Green’s Function Monte Carlo.
J.M. Hammersley and D.C. Handscomb, ”Monte Carlo Methods”, Chapman and Hall, 1964. Clas-
sic monogram on basic Monte Carlo methods.
B. L. Hammond, W. A. Lester, Jr. and P. J. Reynolds, ”Monte Carlo Methods in Ab Intio
Quantum Chemistry” World Scientific, 1994. (541.28015192) Detailed description of variational and
diffusion Monte Carlo applied to small molecules.
5.6.7 Path Integrals

Landau-Paez 309.
5.7 Perturbation Theory, Exercises

5.7.1 Perturbations time independent (non-degenerate case)
1. For the Infinite well, given that H 0 = αδ(x − b) (with 0 < b < a, and a is the width of the well)
compute: a) E (1) , b) E (2) , c) the wave function, to first order (you can give the result as a sum)
and d) do the same for the 1d harmonic oscillator
Z
0 α a α
A: a) En(1) = Hnn = d x sin2 (nπx/a) δ(x − b) = sin2 (nπb/a)
a 0 a
α 2 X sin2 (nπb/a) sin2 (mπb/a) 2mα2 X sin2 (nπb/a) sin2 (mπb/a)
b) En(2) = =
a (n2 − m2 )π 2 /2ma2 π2 n2 − m 2
m6=n m6=n
2. Find the relativistic corrections to the a) infinite potential well and b) to the 1-D harmonic
Oscillator.
p
A: The Hamiltonian for the relativistic H = m2 + p2 − m + V (x) ' p2 /2m − p4 /8m3 +
· · · + V (x) = H0 + H with H = −p /8m . For the infinite potential well the correction is
0 0 4 3
(1) (1)
En = −p4nn /8m3 . p4nn =< n| (−id/d x)4 |n >= (nπ/a)4 and En = −(nπ/a)4 /8m3 .
(1)
For the harmonic oscillator case the correction to the energy is En = −p4nn /8m3 . Given that
(1)
p4nn = (3α4 /2) [n(n + 1) + 1/2] one has that En = −p4nn /8m3 = −(3ω 2 /16m) [n(n + 1) + 1/2]
3. A particle is inside an infinite potential well 1-D, with side a is perturbated by H 0 (x) = eEx.
(1)
Compute En . A:
Z
0 2eE a 1 0 4eEanl
En(1) = Hnn = dx x sin2 (nπx/a) = eEa, Hnl = 2 2 (−1)n−l
− 1
a 0 2 π (n − l2 )2
16meEa2 X nl
(0)
ψn = ψn(0) + (−1) n−l
− 1 ψl
π4 (n2 − l2 )3
l6=n
2 X
4eEa (nl)2 2
En(2) = (−1) n−l
− 1 (5.52)
π2 (n2 − l2 )5
l6=n
4. For the harmonic oscillator potential, corrected by a linear term H 0 = eEx find
(a) The first two corrections to the energy levels. Compare with the exact solution.
(b) The wave function, to first order.
(1) p
A: En =< n|bx|n >= bxnn = 0. And given that xn,n−1 = xn−1,n = n/2mω.
" #
X 0 |2
|Hnk X b2 xnk xkn b2 x2n,n−1 x2n,n+1 b2
En(2) = = = − =−
(0) (0) (0) (0) ω n − (n − 1) n − (n + 1) 2mω 2
k6=n En − Ek k6=n En − Ek
5.7. PERTURBATION THEORY, EXERCISES 151
This problem can be solved

h analytically by rewritingithe Hamiltonian: H = p2 /2m+(1/2)mω 2 x2 +
2
bx = p2 /2m + (1/2)mω 2 x + b/mω 2 − b2 /m2 ω 4 . Than can be solved (as a harmonic oscilla-
tor again!) by shifting the energy levels En → En − b2 /2mω 2 and the same wavefunctions with
x → x − b/mω 2 . In agreement with the former results.
5. Find the corrections to the energy levels produced by an anharmonic potential to the 1-D har-
monic oscillator (see W. Janke and H. Kleinert, Phys. Rev. Lett. 75, 2787 (1995)). For
H 0 = ax3 + bx4 .
(1)
A: At first order En =< n|ax3 + bx4 |n >= ax3nn + bx4nn = bx4nn =. Given that x4nn =
(1)
3[n(n + 1) + 1/2]/2α4 En = 3b[n(n + 1) + 1/2]/2α4 . An analogous calculation can be done for
the lowest levels:
R∞ −ξ 2 [b̄ξ 4 ]dξ
R ∞ 2 −ξ2 4
(1) −∞ e 3b (1) ξ e [b̄ξ ]dξ 15b
E0 = R∞ = , E1 = −∞ R∞ = ,
−∞ e
−ξ 2
dξ 4(mω) 2
−∞ ξ e
2 −ξ 2 dξ 4(mω)2
R∞ 2 2 −ξ 2 [b̄ξ 4 ]dξ
(1) −∞ (−1 + 2ξ ) e 15b
E2 = R∞ = , ···
−∞ (−1 + 2ξ ) e
2 2 −ξ 2
dξ 2(mω)2
(1)
6. Get En for a particle inside an infinite potential well 1-D, with side a perturbed by the potential

0 V0 , , if 0 < x < b < a
H (x) = (5.53)
0, otherwise
7. Two particles are confined inside an infinite potential well os side a. If they interact via H 0 =
Aδ(x1 −x2 ), so they can not be at the same position simultaneously. How is modified its energy?.
A:
2
2 π2 n1 n22
ψn(0)
1 n2
(x1 ,x2 ) = sin(n1 πx1 /a) sin(n2 πx2 /a), En1 n2 = 2
(0)
+
a 2a m21 m22
Z Z a
0 A a
En1 n2 = Hn1 n2 ,n1 n2 = 2
(1)
dx1 dx2 sin2 (n1 πx1 /a) sin2 (n2 πx2 /a)δ(x1 − x2 )
a 0 0
Z
A a A
= dx1 sin2 (n1 πx1 /a) sin2 (n2 πx1 /a) = [2 + δn1 n2 ] (5.54)
2
a 0 8a
(1)
and for example E11 = 3A/8a.
5.7.2 Time independent perturbation (degenerate case)
8. Solve the characteristic equation for the case of two degenerate levels. Solve the case of a
magnetic dipole in an arbitrary constant magnetic field.
A:
Figure 5.3: Figures for the exercises of Perturbation theory


Haa Hab ca ca H − E (1) Hab
=E (1)
, aa =0

Hba Hbb cb cb Hba Hbb − E (1)
h p i
with solution E± = (1/2) Haa + Hbb ± (Haa − Hbb )2 + 4|Hab |2 and c± ± ±
b = − [Haa − E ] cb /Hab .
In the case of the dipole (with spin 1/2) in presence of an arbitrary constant magnetic field, the
Hamiltonian is (µ = |µ|)
1

Bz Bx − iBy −B−
H 0 = −µ · B = −µ , ψ+ = p → ψ↓
Bx + iBy −Bz 2B(B + Bz ) B + Bz

1 B + Bz
ψ− = p → ψ↑
2B(B + Bz ) B+
and E ± = ±µB. In the case the z axis is chosen along the B field the solution reduces appro-
priately.
9. Find the relativistic corrections to the a) 3-D infinite potential box and b) to the 3-D anharmonic
Oscillator. A: H 0 = −p4 /8m3
< p4 > = < (p2x + p2y + p2z )2 >=< p4x + p4y + p4z + 2p2x p2y + 2p2x p2z + 2p2y p2z >

3 X 4 1 1 X
= αi ni (ni + 1) + + αi2 αj2 (2ni + 1)(2nj + 1) (5.55)
2 2 4
i=x,y,z i6=j=x,y,z
10. Show that for a central potential, including the perturbation (H 0 (r) = H 0 (|r|)) the matrix H 0 is
diagonal: Hnlm,
0
n0 l0 m0 =< n|H (r)|n > δll0 δmm0 .
0 0
A:
Z
0 0 0 0 0 ∗
Hnlm, n0 l0 m0 (r) = < nlm|H (r)|n l m >= dV Rnl Ylm H 0 (r)Rn0 l0 Yl0 m0
Z ∞ Z
0 ∗ 0
= [ r drRnl H (r)Rn0 l0 ][
2
Ylm Yl0 m0 ] = Hnl, n0 l0 (r)δll0 δmm0 (5.56)
0 4π
11. Find the relativistic corrections to the a) 3-D infinite potential spherical well, b) to the 3-D
harmonic Oscillator and c) for a hydrogenic atom.
12. Suppose that the Nuclear radio is a ∼ 1 fm, and can be approximate by a uniform sphere
of constant charge density find a) The Electric Potential produced by such model and b) The
Energy corrections produced to the Hydrogen atomic levels. Comment. What happens for large
atomic number, Z?
A: The potential becomes
(
−Zα 3(r/R)2 − 2 /2R if r¡R
V (r) =
−Zα/r if r > R

0 1
H = −Zα 3(r/R) − 2 − 1/r θ(r − R)
2
(5.57)
2R
and the shift for the ground state energy becomes, for the same level n
Z R Z
0 0 0 0 0
Hnlm,nl 0 m0 = < nlm|H |nl m >= δll0 δmm0 r dr Rnl H (r)Rnl0 ' δll0 δmm0 |Rnl (0)|
2 2
drr2 H 0
0
Z
R
1 r 2 1
= −4πZα|ψns (0)| δl0 δll0 δmm0
2
dr 3 −2 −
0 2R R r
" 3 #
32 32 1 Z
= πZα|ψnlm (0)|2 R2 δl0 δll0 δmm0 = πZαR2 δl0 δll0 δmm0
15 15 π naµ

64 ZR 2 (0)
= − En δl0 δll0 δmm0 , Ens (1)
' −4.3 · 10−10 · En(0) (5.58)
15n aµ
that can be compared with the main corrections due to the hyperfine structure:
me (0)
Ehf = α2 E ' −2.8 · 10−8 · En(0) (5.59)
mp n
13. What are the corrections to the atomic levels of the Hydrogen atom produced by the gravitational
interactions, between the nuclei and the electron?. Compute it by using perturbation theory and
compare it with the exact result.
A: H 0 = −GmN me /r and its matrix elements for the level n are
0 GmN me Z
Hnlm,nl 0 m0 = < nlm|H 0 |nl0 m0 >= −GmN me δll0 δmm0 < 1/r >nl = −δll0 δmm0
n2 aµ
Zκ
= −δll0 δmm0 , En(1) = −(Zκ/n2 ) (5.60)
n2
with κ = GmN me /aµ ' 10−39 eV (aµ = 1/αµ) and given that (1/r)n = Z/aµ n2 . An analytical
calculation is possible by noticing that V = −Zα/r − GmN me /r = −Z ∗ α/r with Z ∗ = Z[1 +
(0) (1) (1)
GmN me /Zα]. Thus the spectra is En = −(µ/2)(Z ∗ α/n)2 = En + En + · · · , so En = −κ/n2
in agreement with the results given previously. An explicit calculation for the first levels is
R∞ R ∞ −ρ
(1) e−2ρ [−κ/ρ]ρ2 dρ (1) 0 Re (1 − ρ/2) [−κ/ρ]ρ dρ
2 2
κ
E1s = 0 R∞ = −κ, E2s = ∞ −2ρ =− ,
0 e −2ρ ρ2 dρ
0 e (1 − ρ/2) ρ dρ
2 2 4
R∞
(1) e−ρ [−κ/ρ]ρ4 dρ κ
E2p = 0 R∞ = − ,···
0 e ρ dρ
−ρ 4 4
This effect is very small given that Gmp me /α~c = 5 · 10−40 . Even if this were not the case the
spectra is not modified and the correction is absorbed in the α measurement and therefore it is
not possible to observed it.
14. A hydrogen atom is inside a gravitational field H 0 = mgz. Find the changes in the energy
produced by this field in the levels n = 1 and n = 2. Workout the Stark effect for the n = 2
state of a hydrogenic atom. Hint: H 0 = eEz
(1)
A: For n = 1 there is no degeneracy and E1s = −eE < 1s|x|1s >= 0 (see fig. 7). For n = 2 one
has to compute the matrix H 0 , where the files and rows are ordered as 2s, 2p0, 2p1, 2p − 1:
     
0 A 0 0 0 0
 0 0 0   0   
H0 = 
A     0  → |2p − 1 >
 0 0 0 0  , E = 0, ψ1 =  1  → |2p1 >, ψ2 =  0 
0 0 0 0 0 1
 
1
1   → √1 (|2s > ±|2p0 >)
±1 
E = ±A, ψ3,4 = √  (5.61)
2 0  2
0
Thus two levels remain unshifted (|2p ± 1 >), while the other two get mixed and go up and
down. Notice the the z-component of the angular momenta remains well defined but the total
angular momenta does not.
15. Consider an almost symmetric (in 3-D) harmonic oscillator: V = (1/2)mω 2 [x2 + y 2 + (1 + )z 2 ].
Find the lowest order corrections to the energy and the wave function of the ground state.
A: H 0 = (1/2)mω 2 z 2 so Enx ny nz = (1/2)mω 2 < z 2 >= (1/2)mω 2 [(2nz + 1)/2αz2 ].
16. For a two dimensional infinite well of dimensions a × a, perturbated by H 0 = aδ(x − a1 )δ(y − a2 ),
with 0 < a1 , a2 < a find: a) the first non-vanishing correction to the energy levels, b) the
orthonormal wave functions to lowest order. A: The unperturbated solution is
nπ
(0) π2 (0) 2 lπ
Enl = (n 2
+ l 2
), ψ = sin x sin y (5.62)
2ma2 nl a a a
An considering the two degenerate states: |n = 2, l = 1 > and |n = 1, l = 2 > one obtains

0 A2 AB
H = (5.63)
AB B 2
p p
with A = 4α/a2 sin(2πa1 /a) sin(πa2 /a) and B = 4α/a2 sin(πa1 /a) sin(2πa2 /a). The eigen-
values and eigenvectors are

1 −B 1 A
E = 0, ψ0 = √ , and E = A + B , ψ− = √
2 2
(5.64)
A2 + B 2 A A2 + B 2 B
17. Solve the totally asymmetric rotor, for the state l = 0, 1. Consider that the inertia momenta
are Iz , Ix = Iy − ∆I (Davidov p. 180). What about the symmetries?
" #
1 L2x L2y L2z 1 L2 1 1 ∆I
H = + + = + − L2z + 2 L2x = H0 + H 0
2 Ix Iy Iz 2 Iy Iz Iy 2Ix

(0) 1 l(l + 1) 1 1
Elm = + − m2
2 Iy Iz Iy
∆I 2 a 2
H0 = Lx ≡ aL2x = L+ + L2− + L+ L− + L− L+ (5.65)
2Ix
2 4
(1)
For the no degenerate level l = 0 one can see that Es =< s|H 0 |s >= 0. In the case of the next
(1)
level, |l = 1, m = 0 > one has that Ep0 =< p0|H 0 |p0 >= (a/4) < p0| L2+ + L2− + L+ L− + L− L+ |p0 >=
(a/2) < p0| (L+ L− + L− L+ ) |p0 >= 2a. In the case of the third level degeneracy is present, for
the states |l = 1, m = ±1 > and one has to diagonalize the matrix

0 ∆I 2 a 2 a 1 1
H = Lx ≡ aL2x = L+ + L2− + L+ L− + L− L+ = (5.66)
2Ix
2 4 2 1 1
The eigenvalue equation becomes (a − E)2 − a2 = 0 with solutions (see Fig. 8)

1 1 ∆I 1 1
E = 0, φ0 = √ , and E = a = 2 , φ− = √ (5.67)
2 −1 Ix 2 1
18. Suppose the totally symmetric rigid rotor is perturbated by H 0 = aLx . Consider l = 1
19. Suppose the totally symmetric rigid rotor is perturbated by H 0 = αLz + βLy . Consider l = 1.
A:
 √ 
α√ −iβ/ 2 0√
H0 =  iβ/ 2 0√ −iβ/ 2  (5.68)
0 iβ/ 2 −α
with eigenvalue equation E[α2 − E 2 + β 2 ] = 0. Then the solutions are:
   
1√ p α ±√E+
1
 −iα 2  , 1 
E = 0, φ0 = p and E± = ± a2 + β 2 , φ± = iβ 2 (5.69)
2(1 + |α|2 ) 2E+
1 α ∓ E+
20. How do the energy levels of a hydrogenic atom change due to the Spin-Orbit interaction?
21. Suppose the ‘spin-spin’ (actually is the interaction between their magnetic momenta) interaction
between the nuclei and the electron (in the hydrogenic atom) is H 0 = As1 · s2 . Find the new
levels of the old ground state n = 1. How is this related to the hyperfine structure of these
atoms?. |s1 , m1 > |s2 , m2 > if a) s1 = s2 = 1/2 and b) s1 = 1 y s2 = 1/2
A: Using the fact that if J ≡ s1 + s2 then s1 · s2 = (1/2)[J 2 − s21 − s22 ] one√find that for the first
case the two states are: A triplet (|11 >= | ↑↑>, |10 >= (| ↑↓> +| ↓↑>) / 2 and |11 >= | ↓↓>)
(1) √ (1)
with EJ=1 = −A/4 and a singlet (|00 >= (| ↑↓> −| ↓↑>) / 2) and EJ=0 = −3A/4.
~ · L),
22. Workout the Zeeman effect (H 0 = −(e/2me )B ~ for the state n = 2, without taking into
account the spin.
23. Does the gravitational interaction in the hydrogenic atom break the degeneracy of their energy
levels?. Why yes?, why not?.
24. Raman Spectra, rotational part.
5.7.3 Time dependent perturbation theory, exercises
25. Suppose a plane wave incides on a system such that the interaction is described by H 0 =
C exp (iωt). Find the probability of transition from the state ‘a’ to the state ‘b’, as a function
of time. Discuss the case of resonance, ωba = Eb − Ea
Z t
0 0 ei(ω−ωnn0 )t − 1
cn = −i dt0 e−iωnn0 t Ann0 eiωt = −iAnn0 (5.70)
0 i(ω − ωnn0 )
2
2 sin (ω − ωnn0 )t/2
2
t ω → ωnn0
P (n, t; n0 , t = 0) = 4|Ann0 | → |Ann0 |2
(ω − ωnn0 ) 2 (4t/π)δ(ω − ωnn0 ), for t → ∞
26. A system in the ground state of the harmonic oscillator (1-D) is affected by an external pertur-
bation, given by: a) H 0 = Cθ(t)θ(T − t), b) H 0 = Cδ(t − T ). Find the probability that a time
later the system can be in the first excited state.
b)
Z t
0 iC −iωT C2
c1 = −i dt0 e−iω10 t Cx10 δ(t − T ) = − √ e , P (n = 1, t; n = 0, t = 0) = (5.71)
0 2α 2mω
27. If a system starts in the state ‘a’. Find the probability that after a time later is in the state ‘b’
(P (a, t = 0; b, t) =?) if it is affected by the interaction H 0 = Aθ(t)θ(T − t)
28. A hydrogen atom is affected by an electric field for a time T : H 0 = eEzθ(t)θ(T − t). Find the
probability that it changes from the state (n = 1) to the first exited (n = 2)?.
29. A very fast α particle(with velocity v) pass at a distance b of an atom (in the ground state).
Compute the total probability the atom get excited to the first excited state. See Fig. 9.
A: The distance between the the α-particle and the electron in the atom is R = (vt)î + bĵ + r,
where r is the position of the electron. The interaction is desctibed by the potential
Zα Zα Zα(vtx + by)
V = =p ' p
R b + (vt) + r + 2vtx + 2by
2 2 2 b2 + (vt)2
0 Zα(vtxnm + bynm )
Hnm = p
b2 + (vt)2
Z ∞
vtxnm + bynm
a(t) = −iZα dt p (5.72)
−∞ b2 + (vt)2
30. Find what is the Semiclassical Theory of Radiation.
5.7.4 Semiclassical Approximation (WKB method) and Bohr-Sommerfeld

quantization rules
31. Obtain the lifetime of a particle confined by the potential (Fig. 10). Estimated it for typical
values like V0 = 10 MeV, a = 1 fm.



∞, if r < 0

0 if 0 < r < a
V (r) = (5.73)


V0 if a < r < 2a

0 if r > 2a
A:
Z 2a p p
I = 2 dx 2µ[V0 − E] = 2 2µ[V0 − E] a
a
p p
τ1/2 = (2a/v) exp[I] = 2ma2 /E exp[2 2µ[V0 − E] a] (5.74)
32. Fowler-Nordheim, cold emission by metal, tunnel effect. Liboff 257.
33. A particle with mass m and energy E is bounded in 1-D by a potential of the form (Fig. 11)



∞, if x<0

V x/a if
0 0<x<a
V (x) = (5.75)


V 0 if a < x < 2a

0 if x > 2a
find the lifetime of such particle as a function of its energy E. Work out the case V0 = 10 MeV
and a = 1 fm.
A: x0 V0 /a = E, so x0 = aE/V0
Z Z a Z 2a p
2a p p
I = 2 dx 2µ[V (x) − E] = 2 dx 2µ(V0 /a)[x − x0 ] + dx 2µ(V0 − E)
x0 x0 a

4a p 3p 2 p
= 2µV0 (1 − E/V0 )3/2 + 1 − E/V0 = (5 − 2E/V0 ) 2µV0 a2 (1 − E/V0 )
3 2 3
p
τ1/2 = (2x0 /v) exp[(2/3)(5 − 2E/V0 ) 2µV0 a2 (1 − E/V0 )] (5.76)
34. Compute the lifetime of a particle bounded by a finite spherical well of depth −V0 , with angular
momenta l > 0. Hint: Find the ‘Effective Potential’. Rework the α-decay but with the potential
V (r) = l(l + 1)/2µr2
p
A: The return points are a and b = l(l + 1)/2µE
Z s p Z
b
l(l + 1) l(l + 1) b dr p 2
I = dr 2µ −E = b − r2
a 2µr2 b a r
p p
l(l + 1) p 2 2b
= b − r2 − b log [ b2 − r2 + b] (5.77)
b r
35. Rework the α-decay but having into account the angular momenta.
A: The effective potential is
2(Z − 2)α l(l + 1) 2(Z − 2)α l(l + 1) 2(Z − 2)α l(l + 1)

V = + , V0 ≡ + , + −E =0
r 2µr2 a 2µa2 b 2µb2
Z b s Z b p
2(Z − 2)α l(l + 1) dr
I = dr + −E = l(l + 1)/2µ + 2(Z − 2)αr − Er2
a r 2µr 2
a r
b Z b
p dr

= l(l + 1)/2µ + 2(Z − 2)αr − Er + (Z − 2)α
2 p

a
a l(l + 1)/2µ + 2(Z − 2)αr − Er2
Z p
l(l + 1) b dr
+ p = −a V0 − E
2µ a r l(l + 1)/2µ + 2(Z − 2)αr − Er
2
" #b
(Z − 2)α −Er + (Z − 2)α

− √ sin−1 p
E (Z − 2) α + l(l + 1)E/2µ a
2 2
s " s #b
l(l + 1) 1 l(l + 1) p

− log 2 l(l + 1)/2µ + 2(Z − 2)αr − Er2 + 2(Z − 2)αr + l(l + 1)/µ
2µ r 2µ
a
( " # "
p (Z − 2)α (Z − 2)α − Eb (Z − 2)α − Eb
= −a V0 − E − √ sin−1 p − sin−1 p
E (Z − 2)2 α2 + l(l + 1)E/2µ (Z − 2)2 α2 + l(l + 1)E/2µ
s
l(l + 1) a (Z − 2)αb + l(l + 1)/2µ
− log p (5.
2µ b l(l + 1)(V0 − E)/2µ a + (Z − 2)αa + l(l + 1)/µ
36. Show that the centrifugal potential is negligible in comparison with the coulomb one
A:
Vcent. l(l + 1) r l(l + 1)~c 0.197

= = ' ' 0.07 · l2 (5.79)
VCoul. 2µr 2Zα
2 Zαµr (90/137) · 4
37. Obtain the spectra for the infinite well.

A: For a given energy the return points are the walls of the well, x = 0 and x = a. Bohr-
Sommerfeld quantization rules are, then (V (x) = 0 inside the well)
2
√ 1 (n + 1/2)π
2mE a = (n + 1/2)π, En = (5.80)
2 2ma2
that is close to the analytical result, specially for large n, the classical limit.
38. Obtain the spectra for the harmonic oscillator.
A:pThe return points are obtained by solving the equation 2E = mω 2 x2 , so x = ±a =
± 2E/mω 2 . Bohr-Sommerfeld quantization rules become in this case
Z Z
a p ap
1h p 2 ia
2m (E − mω 2 x2 /2)dx = 2mω a2 − x2 dx = 2mω x a − x2 + a2 sin−1 (x/a)
−a 0 2 0
= mωa2 π = (n + 1/2)π, En = (n + 1/2)ω (5.81)
the analytical result.

39. Find the energy spectra for the potential V (x) = ∞ if x < 0 and V (x) = F x for x > 0 . Compare
wit the exact solution given in the exercises of chapter 1.
A: The return points are obtained by solving the equation E = F x, so x = a = E/F . The other
return point is x = 0. Bohr-Sommerfeld quantization rules become in this case
Z ap √ Z a√
2√
2m (E − F x) dx = 2mF a − x dx =
2mF a3/2 = (n + 1/2)π
0 0 3
2/3
3π F F 2/3 3π 2/3
En = (n + 1/2) √ = √ n , n = (n + 1/2) (5.82)
2 2m 2m 2
0
‘Analitic
ns 2.3381 4.0879 5.5206 6.7867 7.9441 9.0226
Numer.
ns 2.3380 4.0878 5.5204 6.7863 7.9436 9.0216
Semic.
ns 2.32 4.08 5.52 6.78 7.94 9.02
Numer.
np 3.361 4.884 6.208 7.406 8.515 9.558
Semic.
np 3.26 4.83 6.17 7.37 8.49 9.54
|u00np (0)|2 (Numer.) 2.2 3.7 5.0 6.2 7.2 8.2
|u00np (0)|2 (Semic.) 1.45 2.15 2.74 3.28 3.77 4.24
Table 1:‘Exact’ (root of the Airy funtion), numerical and Semiclasical results, for l = 0, 1. See
C. Quigg and J. Rosner, Phys. Rep. 56, 167 (1979))
40. Obtain the spectra for the potential V (x) = F |x|.
A: The return points are obtained by solving the equation E = F |x|, so x = ±a = ±E/F .
Bohr-Sommerfeld quantization rules become in this case
Z ap √ Z a√
4√
2 2m (E − F x) dx = 2 2mF a − x dx = 2mF a3/2 = (n + 1/2)π
0 0 3
2/3 2/3
3π F F
En = (n + 1/2) √ = √ n (5.83)
4 2m 2 2m
41. Obtain the spectra for the anharmonic oscillator V = F x4 .
A: Given that the return points are x = ±a = ±(E/F )1/4
Z a p √ Z 1 p
2m (E − F x4 ) dx = 2mEa2 1 − t4 dt = (n + 1/2)π
−a −1
4 F 1/3 Z 1p
4 π
En = (n + 1/2) , c = 1 − t4 dt = 1.748038 · · · (5.84)
c 4m2 −1
Thus E0 = 0.55 · (F/m2 )1/3 , E1 = 2.38 · (F/m2 )1/3 and so on.

42. Obtain the spectra for the anharmonic oscillator V = F xr θ(x).
A: Given that the return points are x = 0 and x = (E/F )1/r
Z ap √ Z 1√
2m (E − F xr ) dx = 2mF ar+2 1 − tr dt = (n + 1/2)π
0 0
2r/(r+2) Z
(n + 1/2)π 1√
En = F √ , cr ≡ 1 − tr dt (5.85)
2mF cr 0
√ √
Thus E0 = F (π/2 2mF cr )2r/(r+2) , E0 = F (3π/2 2mF cr )2r/(r+2) and so on.
43. Obtain the spectra for the potential V (r) = ∞ if r < 0 and F log(r/r0 ) when 0 < r
44. For the Hydrogen atom with angular momenta l, using the ‘Effective Potential’ (Compare with
the method used by Sommerfeld to explain the fine structure. See Eisbergs book)
A: In this case we have two quantization rules: l = nθ = 1, 2, 3, · · · and
I a
µ Zα 2 (Zα)2 1 3
pr dr = l − 1 = nr = 0, 1, 2, 3, · · · , En = − 1+ − (5.86)
b 2 n n nθ 4n
with the principal quantum number n = nθ + nr . The second terms give us the fine structure,
obtained by the first time by Sommerfeld around 1919.
45. Bohr-Sommerfeld in 3-D. Park and Rosner p. 196-99, ref. pie pagina 196. See Phys. World
Jan.-98, p. 29.
5.7.5 Variational Principle
46. Obtain the ground state energy for the infinite well.
A: Let’s try the function ψ = Axα (x − a). The norm and the expectation value of d2 /dx2 are
Z a
1
dx|ψ|2 = |A|2 a2α+3
(2α + 3)(α + 1)(2α + 1)
Z a0
−α
dxψ ∗ ψ 00 = |A|2 a2α+1 2
0 4α − 1
1 α(2α + 3)(α + 1)(2α + 1)
E(α) = (5.87)
2ma2 4α2 − 1
One can find a solution a minima for α = 1.0430653 with E = 9.97928 · /2ma2 > E0an. =
π 2 /2ma2 = 9.8696044/2ma2 . Notice that additional minimae are obtained for α < 0.5! (?)
47. Obtain the spectra for the harmonic oscillator,

A: a) For the harmonic oscillator, for the ground state a good choice for the wavefunction can
√
be ψ = A exp[−aξ 2 ] with ξ = mω x. Then
Z Z
1 d2
† 1 ω|A|2 2
< φ|H|φ > = dxφ − + mω x φ =
2 2
dξe−2aξ 2a + (1 − 4a2 )ξ 2
2m dx 2 2 2
r
ω|A| 2 1 π ω
= 2a + (1 − 4a2 ) = [a + 1/4a]
2 4a 2a 2
that has a minima for a = 1/2 and E = ω/2, ψ = Ae−ξ/2 .
48. Find the ground state energy for the potential V (x) = ∞ if x < 0 and V (x) = F x for x > 0
(see applications to the Quarkonium in C. Quigg and J. Rosner, Phys. Rep. 56, 167 (1979)).
Compare with the exact solution given in the exercises of chapter 1.
A: One can take the trial function as pe. ψ = Ax exp[−αx] (that satisfy the boundary conditions)
so
R∞
dx xe−αx −(α/2m) (αx − 2) + F x2 e−αx (2α)3 1 2α 2!α2 3!F
E = 0 R∞ = − +
0 dx xe
−2αx 2! 2m (2α)2 (2α)3 (2α)4
α2 3F
= + (5.88)
2m 2α
√ √
it has a minima for α = (3mF/2)1/3 with E = (35/3
√ /24/3 )(F/ 2m)2/3 = 2.48(F/ 2m)2/3 to be
compared with the numerical result E = 2.34(F/ 2m)2/3
49. Obtain the ground state energy for the potential V (x) = F |x|.
50. Obtain the spectra for the potential V (r) = F r in 3D.

A: It was done with the oscillator wavefunction K. Novikov, Phys. Rev. D51, 5069 (1995).
51. Obtain the ground state energy for the anharmonic oscillator V = F x4 .
A: One can choose the trial function ψ = A exp[−αx2 /2] so
R∞ −αx2 /2
2
−∞ dxe (−1/2m)d2 /dx2 + F x4 e−αx /2
<E> = R∞
−∞ dxe
−αx2
r Z
α ∞ −αx2
√ 1 α2 α 3
= dx e (−1/2m)(α x − α) + F x = α −
2 2 4
√ −√ +F 2
π −∞ 2m 2α α α 4α
α 3F
= + (5.89)
4m 4α2
There is a minima at α = (3mF )1/3 , and the value obtained for the ground state energy is
E0v.p. = (3F/m2 )1/3 /2 = 0.72(F/m2 )1/3 that compares correctly with the value obtained by the
Bohr-Sommerfeld quantization rules E0BS = 0.55(F/m2 )1/3
52. Obtain the ground state energy for the anharmonic oscillator V = F xr θ(r).
A: One can choose the trial function ψ = Ax exp[−αx] that satisfy the boundary conditions
R∞ R∞
(−1/2m) dxe−2αx (α2 x2 − 2αx) + F dxe−2αx xr
<E> = 0 R∞ 0
0 dxe
−2αx x2
α2 F
= + (r + 2)! (2α)−r (5.90)
2m 2
There is a minima at α = (1/2)[rF (r + 2)!/m]1/(r+2) , and the value obtained for the ground
state energy is E0v.p. =?
53. Obtain the ground state energy for the potential V (r) = ∞ if r < 0 and F log(r/r0 ) when 0 < r
54. For the Hydrogen atom with angular momenta l, using the ‘Effective Potential’ (Compare with
the method used by Sommerfeld to explain the fine structure. See Eisbergs book)
55. Find the ground state of a heliumlike atom (an atom or ion with an atomic number Z and two
electrons.
A: The hamiltonian for this system is:
1
H=− ∇21 + ∇22 − Zα (1/r1 + 1/r2 ) + α/r12 (5.91)
2m
For the ground state one can use the trial function ψ = (a3 /8π) exp[−a(r1 + r2 )/2], already
normalized. Thus
< ∇21 > = < ∇22 >= −a2 /4, < 1/r1 >=< 1/r2 >= a/2
Z Z
−a(r1 +r2 )
< 1/r12 > = [a /8π]
3 2
d r1 d r2 e
3 3
/r12 = [a /8π]
3 2
d3 r1 dr2 r22 · 2πe−a(r1 +r2 )
X r− l Z 1 Z
l
· l+1
d cos θ Pl (cos θ) = [a /16π] · 4π
6
dr1 r12 dr2 r22 · e−a(r1 +r2 )
r −1 r+
l≥0 +
Z Z Z
a6 ∞ r1
r2 ∞
= dr1 r12 dr2 2 · e−a(r1 +r2 ) + dr2 r2 · e−a(r1 +r2 )
4 0 0 r1 r1
Z
a6 ∞ 1 2 −2ar −ar
−2ar
= dr r − r /a + 2r/a + 2/a · e
2 2 3
+ 2e /ra + r/a + 1/a · e
3 2
4 0 r
a6
= 2/a5 − 1/4a5 − 1/2a5 = 5a/16 (5.92)
4
so the expectation value of the Hamiltonian becomes
< H >= a2 /4m − (Z − 5/16) αa, E = −m [(Z − 5/16)α]2 (5.93)
given that it has a minima at a = (Z − 5/16) · 2mα. The factor 5/16 is a rough measure of the
mutual screening of one electron over the other. See Park 486.
5.7.6 Numerical Methods
56. Solve numerically the potential V = F x4
57. Solve numerically the potential V = −V0 δ(x − a) (Landau 231).
58. Workout numerically the collision of a wavepacket (pe. a gaussian one) with a rectangular wall.
59. workout the Hartree-Fock case done in Kooning 65

Chapter 6
Topics in Atomic Physics
6.1 Hydrogenic atoms
6.1.1 Nuclei mass
The hidrogenic atom spectra is
2
µ Zα
En = − (6.1)
2 n
In the case of hydrogen the correction is ∆E/E ' me /mp ' 5.4 · 10−4 . However for positronium
is as large of 50%. Historically this effect was used by H. C. Urey to discover Deuterium in 1932 by
observing the shift of its spectral lines with respect to the normal hydrogen [Hadronic atoms].
6.1.2 Relativistic corrections at order (Zα)2
Relativistic effects are controlled by the size of the average speed, of the order of (Zα)2
2
∆E Zα
'v =
2
' 0.5 · 10−5 (6.2)
E E.F. n
where α ∼ 1/137.035, the fine structure constant. The complete theory is the Dirac equation (or
better the QED), however a good approximation is obtained by using the Schrödinger-Pauli Equation
plus the relativistic effects treated as perturbations. In general the hamiltonian for a bounded system
of two different particles can be described by the Breit-Fermi one (Bethe-Salpeter 193, Donoghue 129,
335 and Lucha 198) [NRQM, 23, 25]
165
166 CHAPTER 6. TOPICS IN ATOMIC PHYSICS
5 5
p2 αeff X X
H = − + Hi = H0 + Hi
2µ r
i=1 i=1

1 p41 p42 p4 1 1
H1 = − + =− +
8 m31 m32 8 m31 m32

iαeff p1 p2 1 αeff
H2 = − − 2 ·∇ + [p1 · p2 + r̂ · (r̂ · p1 p2 )]
8 2
m1 m2 r 2m1 m2 r

παeff 1 1 αeff 2
= + 2 δ (3) (r) − p + r̂ · (r̂ · pp)
2 m 2 m2 2m1 m2 r
1
παeff 1 1 αeff 2 2 1 2 2 1
= + δ (r) −
(3)
p − 3L + p , − 4πδ (r)
(3)
2 m21 m22 2m1 m2 r r r

αeff l1 · s1 l2 · s2 αeff αeff L · s1 L · s2 αeff L · s
H3 = − + (l1 · s2 − l2 · s1 ) = 3 + +
2r 3 m1 2 m22 m1 m2 r 3 2r m12 m22 m1 m2 r3
8παeff (3) αef f
H4 = δ (r)s1 · s2 − T, with T = s1 · s2 − 3(s1 · r̂)(s2 · r̂)
3m1 m2 m1 m2 r3
παeff 2 (3)
H5 = s δ (r) (6.3)
m1 m2
where αeff = −Zαe1 e2 , r = |r|, r̂ = r/r, ei is the charge of the respective particle in proton charge
units and in the CM p1 = −p2 = p and L = l1 = −l2 = r ∧ p.
1. The first term correspond to relativistic correction to the kinetic energy.
2. The second takes into account the time light takes to travel from one particle to the other
particle.
3. The third is the so called ‘spin-orbit’ interaction. It is due to the interaction between the magnetic
field generated by the rotating electron (l > 0) and its own magnetic momenta (µ = ge (e/2me )
with ge ∼ 2.00). This is the so called spin-orbit interaction and its Hamiltonian is (Eisberg-
Resnick p. 304, Bjorken p. 51 and Itzykson p. 71).
4. The fourth is the so called ‘spin-spin’ interaction and the
5. fifth one takes into account the possible annihilation of the two particles in the case it is possible.
Let us work them out using relations as (all are diagonal)
−1 1 αeff. µ −2 1 (αeff. µ)2 δl0 αeff. µ 3

rnlm = = , r = = , |ψ nl (r = 0)| 2
=
aµ n2 n2 nlm a2µ n3 (l + 1/2) n3 (l + 1/2) π n
α µ 3 3 h i
−3 eff. 1 1 1 αeff.
rnlm = · = , p2 = 2µ H0 +
n l(l + 1/2)(l + 1) aµ n l(l + 1/2)(l + 1) r

1 2i 1
L2 = r2 p2 + 2ir · p − r (r · pp) , p2 , = 4πδ (3) (r) + 3 r · p, p2 , =0 (6.4)
r r r nn
where 4(1/r) = −4πδ (3) (r), aµ = 1/µαeff. is the Bohr’s radius.

6.1. HYDROGENIC ATOMS 167
Kinetic energy corrections

Using the expression for p2 one obtains that

µ2 1 1 1 1
∆E1 = − + 3 En + 2αeff. En
2
+ αeff.
2
2 m1 m23 r r2 nlm
nlm
1 1 3 n αeff. 2
= −µ3 + · − En (6.5)
m31 m32 4 l + 1/2 n
where En is the lowest order energy (Bohr’s spectra).
Retardation time contributions

Darwin’s term. The physical origin of this term can be imagined as the impossibility for the electron of
be in the same place of the proton and is only present for the s-states (l = 0), where the probability that
this happens is nonzero. Mathematically can be traced back to the normalization of the wavefunction.
The correction is (Bransden p. 641, Bjorken p. 52 and Itzykson p. 71)

1 1 (αeff µ)2 3n (αeff µ)2
∆E2 = − + 2 En δl0 − 2 − + 4nδl0 En (6.6)
2
m1 m2 n l + 1/2 m1 m2 n2
6.1.3 Case m2 > m1

In this case it is convenient to use the JJ scheme, J = L + s1 + s2 ≡ J1 + s2 . The wavefunctions can
be characterized as |njmj , lj1 s1 s2 >→ n2j1 lj . In this case the annihilation term vanish and in order
to compute the spin terms one can use the identities (in this scheme)

1 2 1  0 l=0
L · s1 = J1 − L2 − s21 = l, j1 = l + 1/2 (6.7)
2 2
−l − 1, j1 = l − 1/2
To compute the other expectation values for the terms proportional to L · s2 , (s1 · x)x and s1 · s2
one can show that L, (s1 · x)x and s1 are vector, with respect to J1 to obtain (see exercises, or using
the Wigner-Eckart theorem)

2
hL · J1 J1 · s2 i J1 + L2 − S12 J 2 − J12 − S22
hL · s2 i = =
J1 (J1 + 1) 4J1 (J1 + 1)

2 2
h(s1 · x)x · J1 J1 · s2 i (s1 · x)2 J1 · s2 x J − J12 − S22
h(s1 · x)x · s2 i = = =
J1 (J1 + 1) J1 (J1 + 1) 8J1 (J1 + 1)

2 2 2
2 2 2

hs1 · J1 J1 · s2 i L − J1 − S1 J − J1 − S2
hs1 · s2 i = =
J1 (J1 + 1) 4J1 (J1 + 1)

2 2
J1 + S1 − L − 3/2 J − J12 − S22
2 2
hT i = (6.8)
4J1 (J1 + 1)
given that x · L = 0 and the fact that si = σi /2 The contribution with G = L − s1 + 3(s1 · r̂)r̂ and
can be reduced by (see exercises for the reduction G · J1 = L2 )

1 1 1 1 1 2 l(l + 1) 1
G · s2 = G · J1 J1 · s2 = L J · s2 = hJ1 · s2 i
r3 J1 (J1 + 1) r3 J1 (J1 + 1) r3 J1 (J1 + 1) r3
2(αef f µ)2 En j(j + 1) − j1 (j1 + 1) − s2 (s2 + 1)
= − · (6.9)
m1 m2 n (2l + 1)J1 (J1 + 1)
and the corrections to the energy are, then
2
∆E 3 n 1 δl0 j1 (j1 + 1) − l(l + 1) − s1 (s1 + 1) µ 2m1
= − − − − 1+
2 E
αeff n 4 l + 1/2 n 2 n nl(l + 1)(2l + 1) m1 m2
8µ2 2µ2 [j(j + 1) − j1 (j1 + 1) − s2 (s2 + 1)]
− δl0 [j(j + 1) − s1 (s1 + 1) − s2 (s2 + 1)] −
3m1 m2 n m1 m2 n (2l + 1)j1 (j1 + 1)
2
3 n 1 j1 (j1 + 1) − l(l + 1) − s1 (s1 + 1) m1 /m2
= − − −
4 j1 + 1/2 n2 nl(l + 1)(2l + 1) 1 + m1 + m2
2µ [j(j + 1) − j1 (j1 + 1) − s2 (s2 + 1)]
2
− (6.10)
m1 m2 n (2l + 1)j1 (j1 + 1)
where the last expression is valid in the case of s1 = 1/2
Fine structure
2 E . There are three contributions of this order: the relativistic
The fine contribution is of the order αeff. n
corrections to the kinetic energy, the Darwin term and the spin-orbit to have

α2 En 3 1
Efine = − eff. − (6.11)
n 4n j + 1/2
A similar expression was obtained by Sommerfeld by assuming elliptical orbits (Eisberg-Resnick p.
127) with j + 1/2 = nθ , a new quantum number. It should be observed that the degeneracy is partially
removed. A more complete theoretical answer is provided by the Dirac equation (Merzbacher p. 607,
Schiff p. 471, Bjorken p. 55, Bethe, Rose, Itzykson p. 75, Brasden p. 201)
 
 !2 −1/2 
 α 
Dirac
Enj = m 1 + p eff.  −1 , with κ = J + 1/2

 n − κ + κ2 − (αeff. )2 


1 αeff. 2 1 αeff. 4 3 n
' m 1− + − + ··· − 1 (6.12)
2 n 2 n 4 j + 1/2
with αeff = Zα << 1. This expression is in agreement with the formula obtained before. The
fine structure of the energy spectra is shown in Fig. 1 (the spectral notation n2s+1 lJ has been used)
and the optical structure for the Hα line is shown in the Fig. 2. In general due to the line width the
lines become nf (the final principal quantum number) lines: a singlet for the Lyman, a doublet for
the Balmer, a triplet for the Paschen, a quartet for the Brackett, 5 for the Pfund, etc.
. . . . . . . . . . . . . . . . . . . . . . . . . . Ionization
................................
2p3/2 , 2d3/2
3s, 3p, 3d Hydrogenic atoms
2p3/2 , 2d1/2
2s1/2 , 2p1/2
2p3/2 , f =2
2p3/2 , f =1
2p3/2 2s1/2 , f =1
2s, 2p 2p3/2 2s1/2 2s1/2 , f =0
2s1/2 , 2p1/2 2p1/2 1057 Mhz 2p1/2 ,
6 f =1
2p1/2 , f =0
1s1/2 1s1/2 1s1/2 , f = 1

1s
1s1/2 , f = 0 61420 Mhz
Bohr’s Fine Lamb Hyperfine
Figure 6.1: Schematic representation of the energy levels of hydrogenic atoms, in the Bohr’s, Fine
structure, Lamb shift, hyperfine energy approximations. n2S+1 LJ
6.1.4 Lamb-Retherford shift at order α(Zα)2

1. Lamb-Retherford shift is the splitting between levels with the same angular momenta (J), but
different orbital angular momenta (l). Those states are degenerate according to Dirac theory,
but due to Quantum Field (QED) effects this degeneracy is broken.
2. Such possibility was already suggested in 1928 by Grotrian (Branden AM 229) when he proposed
to measure the transition 2p3/2 − 2s1/2 using radio waves to test the Sommerfeld predictions for
fine structure.
3. In 1937 W. Houston and in 1938 R. Williams realized optical experiments, that were interpreted
by S. Pasternack in 1938 as the splitting of the levels 2p1/2 − 2s1/2 , in contradiction with the
Dirac’s theory.
4. Unfortunately the experiments were not conclusive about the presence or not of this splitting,
due to the poor resolution of the optical experiments of that time.
5. In 1947 Lamb-Retherford were able to measure by the first time the splitting between the states
2s1/2 and 2p1/2 , in a conclusive manner by using microwaves [Lamb]. They got ∆ν = 1057.77(1)
Mhz, with the state 2s1/2 above the 2p1/2 (see Fig. 4). They measured the splitting for deuteron
too: ∆ν = 1059.00(1) Mhz.
6. From the theoretical side the first results in the 30-s (Weisskopt in 1934) was a disaster: the
obtain divergent integrals.
Effect ∆ν[Mhz]
Vacuum polarizarion -27
Electron mass renormalization 1017
Anomalous magnetic moment 68
Total 1058
Table 6.1: Main contributions to the energy splitting of the 2s1/2 and 2p1/2
7. Fortunately the final explanation was given by the Quantum Electrodynamics (QED), once the
radiative corrections are included properly or as it is called: renormalization.
8. This program was implemented by Tomonaga Feynman, Schwinger, etc [23].
9. The first attempt was done by Welton [Lamb] in 1948 who computed the corrections due to the
vacuum fluctuations of the Electromagnetic Fields (Bjorken 59, Itzykson 81), obtaining
4 mα(Zα)4
∆E = E(2s1/2 ) − E(2p1/2 ) = − [log(Zα)]δl0 ' 660 Mhz (6.13)
3π n3
10. A more careful calculation result is (See Itzykson 358, Bjorken 177) [Lamb]
(
4 me α(Zα)4 log[m/2 < En0 >] + 19/30, if l = 0
∆Enl = ·
3π n3 log[m(Zα) /2 < Enl >] + 3Clj /8(2l + 1) if j = l 6= 0
2
(
me α(Zα)4 k(n, 0) if l = 0
∆E = · (6.14)
4n3 k(n, l) ± 1/π(j + 1/2)(l + 1/2) if j = l ± 1/2
where Clj = 1/(l + 1) and Clj = −1/l for j = l ± 1/2 respectively. Similarly < E2s >=
16.64 · mα2 /2 and < E2p >= 0.9704 · mα2 /2. The values for 12.7 < k(n, 0) < 13.3 and k(n, l >
0) < 0.05, thus it is significant for s-states.
11. Now it is possible to separate both lines for the Hα line by using the Saturation spectroscopy
technique, due to A. Schawlow Nobel 1981.
Hyperfine structure
1. The hyperfine structure was observed by the first time by Michelson in 1891 and later by C.
Fabry and A. Perot in 1897.
2. the theoretical explanation was given by Fermi in 1924, who postulated that the nuclear magnetic
momenta produces a magnetic field and it interacts with the electron due to its electric charge
and its magnetic momenta (see Fig. 3).
3. The order of magnitude of this corrections is ∆E ∼ α2 (me /mp ) En , so it is smaller than the fine
structure correction by an additional factor of me /mp ∼ 1/2000, for the hydrogen atom.
Element νexp. [Mhz] νtheo. [Mhz]

H 1057.8446 (29) 1057.851 (2)
D 1059.2337 (29) 1059.271 (25)
He+ 14041.13 (17) 14041.18 (13)
C5+ 780.1 (80) GHz 782.87 GHz
phosphorus 20 188 (29) GHz 20 254(10) GHz
L1S H 8172.837 (22) 8172.731 (40)
L1S D 8183.966 (22) 8172.811 (32)
L1S , U91+ 460.2 (46) eV 463.95 (50) eV
Mg11+ 1s1/2 − 2p1/2 0.842 50(4) nm
Mg11+ 1s1/2 − 2p3/2 0.841 90(2) nm
Table 6.2: Lamb shift for hydrogen and other elements [Lamb]
.

H, 1s 1420.405 751 766 7(10) 1420.452
D, 1s 327.384 352 522 (2) 327.339
Tritium, 1s 1 516. 701 470 773 (8) 1516.760
3 He+ , 1s 8665.649 867 (10) 8667.494
µe 4463.302 776 (51) 4463.302 913 (511)(34)(220)
e− e+ 203 389.10 (74) 203 392.01(46)
H, 2s 177.556 860 (16) 177.556 8381(4)
D, 2s 40.924 454 (7) ?40.918 81
3 He+ , 2s 1083.354 980 7 (88) ?1083.5853
e− e+ 2S 8624(3)
Table 6.3: Hyperfine splitting for hydrogen and other elements.

νH (2S1/2 − 1S1/2 ) 2466 061 413.187 103 (46) 2466 061 413.187 103(46)
(νD − νH )(2S1/2 − 1S1/2 ) 670 994.334 64 (15) 670 999.586 6(15)(15)*
νµ+ e− (2S1/2 − 1S1/2 ) 2455 528 941.0(98) 2455 528 935.4(14)
Table 6.4: 2S − 1S transitions. * rd2 − rp2 = 3.8212(15) fm2 [Lamb]

4. For atoms like positronium, muonium and quarkonium this factor is one and fine structure and
hyperfine structure are of the same size and have to be taken into account at the same time.
5. The most important term is given by the nuclear magnetic dipole momenta, but there are
additional factors like [hyperfine]: 1) nucleia mass, 2) nonzero nuclear radius, 3) higher order
multipolar momenta of the nucleia. Here we only take into account the first (Bransden p. 233,
Gasiorowicz p. 277, Griffths p. 158, Eisberg p. 439, Bethe ). The nuclear (electron) magnetic
dipole is
µN = gN µN sN µe = −ge µB se (6.15)
with µN = e/2mp = 5.051 · 10−27 Jul./Tesla = 3.16 · 10−8 eV/Tesla is the nuclear magneton, sN
is the nuclear spin and gN is the gyromagnetic ratio: gp = 2 · 2.79278 and gn = 2 · (−1.91315)
[4]. Similarly for the electron µB = e/2me = 2.274 · 10−24 Jul./Tesla = 5.8 · 10−5 eV/Tesla is
the Bohr magneton, s is the electron spin and ge = 2.00232 its the gyromagnetic ratio. Since
the proton is spin 1/2, and hence every energy level associated with a particular set of quantum
numbers |n, l, j > will be split into two levels of slightly different energy, depending on the relative
orientation of the proton magnetic dipole with the electron state. The new states change from
|njmj , lse > to |nf mf , jlse sN >.
gN me Zα2 f (f + 1) − sN (sN + 1) − j(j + 1)

∆E = − En (6.16)
2mp n j(j + 1)(l + 1/2)
6. Figure 7 shows a revised version of the structure of the hydrogen atom, including the Lamb shift
and hyperfine structure.
7. Note that each hyperfine state still has a 2f + 1 degeneracy associated with the different possible
values of mf .
8. For example, in the ground state, the higher-energy state f = 1 is actually a triplet, consisting
of three degenerate states, and the f = 0 state is a singlet.
9. This degeneracy can be broken by the presence of an external magnetic field. For the specific
case of the ground state of the hydrogen atom [hyperfine] (n = 1), the energy separation between
the states of f = 1 and f = 0 is (see Fig. 4) is of the order ν = 1420 Mhz' 5.9 · 10−6 eV, or the
famous ‘21 cm line’ which is extremely useful to radio astronomers for tracking hydrogen in the
interstellar medium of galaxies.
10. The transition is exceedingly slow, but the huge amounts of interstellar hydrogen make it readily
observable. It is too slow to be seen in a terrestrial laboratory by spontaneous emission, but
the frequency can be measured to very high accuracy by using stimulated emission, and this
frequency is in fact one of the best-known numbers in all of physics. T ' 6 · 10−6 eV/8.6 · 10−5
eV/o K' 0.1 o K.
6.1.5 Case m2 = m1 = m
In this case the hamiltonian becomes
4
p2 αeff X
H = + + Hi
2µ r
i=1
1 παeff (3) αeff 2
H1 = − 3 p4 , H2 = δ (r) − p + r̂ · (r̂ · pp)
4m m 2 2m r2
3αeff 8παeff (3) αef f
H3 = l · s, H4 = δ (r)s1 · s2 − 2 3 T
2m r
2 3 3m 2 m r
παeff 2 (3)
H5 = s δ (r) (6.17)
m2
and it is convenient to use the LS scheme, with J = L + s1 + s2 ≡ L + S. The wavefunctions are
then |njmj , lss1 s2 >→ n2s+1 lj . Using the relation

 l, for j = l + 1
< L · S > = (1 − δl0 )(1 − δs0 ) −1, for j = l

−l − 1, for j = l − 1
1 1
<T > = 6 < L · S >2 +3 < L · S > −2L2 S2 (1 − δl0 )(1 − δs0 ) (6.18)
2 4l(l + 1) − 3
The energy (with En = −(m/4)(αef f /n)2 )

3 n αeff. 2
E1 = − − En
4 l + 1/2 2n

3n αeff 2
E2 = − 6nδl0 + 2 − En
l + 1/2 2n
3α2 En <L·S>
E3 = − eff. ·
2n l(l + 1)(2l + 1)

2αef f En
2
3
2 E
αef f n <T >
E4 = − s(s + 1) − · δl0 −
3n 2 n l(l + 1)(2l + 1)
α 2
E5 = −En · eff. s(s + 1)δl0 (6.19)
2n
and
2
11 3 2 αeff. En
E1 + E2 = − + δl0 −
16n 2 2l + 1 n
2
αef f En 7 α2 En 3 < L · S > −2 < T >
E3 + E4 + E5 = − s(s + 1) − 1 δl0 − eff. · (6.20)
n 6 2n l(l + 1)(2l + 1)
and
line νexp. [MHz] νthe. [MHz]

13 S1 − 11 S0 203 389.1(7) 203 392.1(5)
23 S1 − 13 S0 1233 607 216.4(3) 1233 607 216.4(3)
23 S1 − 23 P0 18 499.7(42) 18 498.4(1)
23 S1 − 23 P1 13 012.4(17) 13 012.6(1)
23 S1 − 23 P2 8624(2) 8626.9(1)
23 S1 − 21 P1 11180(6) 11185.5(1)
23 S1 − 21 S0 - 25 424.69(6)
Table 6.5: Ps transitions
2 E
αeff. n 11 1 2
∆Enjl = − + δl0 − + lsj ,
n 16n 2 2l + 1

(3l + 4)/(l + 1)(2l + 3) if j = l + 1
7 1 − δl0 
l, s=1, j = δl0 + −1/l(l + 1) if j = l (6.21)
3 2l + 1 
−(3l − 1)/l(2l − 1) if j = l − 1
and l, s=0, j = 0. Or(Bethe-Salpeter 117, Itzykson 493-508, Akhiezer 532)

(3l + 4)/(l + 1)(2l + 3) if j =l+1
2αeff.
2 E
n 11 1 7 1 − δl0 
∆Enjl = − + lsj − , l, s=1, j = δl0 + −1/l(l + 1) if j =(6.22)
l
3n 32n 2l + 1 6 2(2l + 1) 

−(3l − 1)/l(2l − 1) if j =l−1
and l, s=0, j = 0. For example

7mα4 α 32 6
E(1 s1 ) − E(1 s0 ) =
3 1
1− + ln 2 + · · · (6.23)
12 π 21 7
6.2 Hydrogenic atoms in external fields

6.2.1 Zeeman effect
It was observed by the first time by P. Zeeman in 1896. It consists in the splitting produced by an
external magnetic field. The Hamiltonian for this case is, with A in the Coulomb gauge (∇ · A = 0)
e e2 2
H0 = A·p+ A + ge µB s · B (6.24)
m 2m
with ge ' 2 for the electron. In the case the magnetic fields doesn’t change appreciably over atomic
distances A = B ∧ r/2 and
6.2. HYDROGENIC ATOMS IN EXTERNAL FIELDS 175
67 eV
. . . . . . . . . . . . . . . . . . . . . . . . . . Dissociation
. . . . . . . . . . . Energy
.....................
6 23 S1
21 P1 23 P1 23 P2
5 23 P0
21 S0
4
3
Positronium: e−e+
2
1 13 S1
0 11 S0
J P = 0− 1− 1+ 0+ 1+ 2+
611 GeV
Υ(11020) Bottomonium: bb̄
Υ(10860)
10.6 Υ(4s)
..........................................................
B B̄ Threshold
.................. Υ(3s)
ηb (3s) ..................
10.2 hb (2p) χb0 (2p) χb1 (2p) χb2 (2p)
.................. Υ(2s)
ηb (2s) ..................
hb (1p) χb1 (1p) χb2 (1p)
9.8 χb0 (1p)
9.4 .................. Υ(1s)

ηb (1s)
J P C = 0−+ 1−− 1+− 0++ 1++ 2++
Figure 6.2: Positronium and Bottonium energy levels comparison. Notice the energies involved.
n2S+1 LJ
e e2 h 2 2 i
H0 = B · L + g e µB s · B + r B − (r · A)2 ' µB (L + 2s) · B (6.25)
2m 8m
for ‘weak’ fields :
e2 A2 /2m
' a20 eB/4 ∼ B/106 Teslas (6.26)
aA/m
Normal Zeeman effect

If the field is strong enough so the produced splitting is very small in comparison with the fine structure,
Tesla
∆EEF /∆EZeeman ' << 1 (6.27)
B
so in this case one can ignore the Fine structure of the spectra and the energy shift of the spectra
are given as
∆Enml ms =< nlml , sms |H 0 |nlml , sms >= µB B(ml + 2ms ) (6.28)
The result is the splitting of the spectral lines in the Lorentz triplet, as it is shown in the Fig.
6. It was called normal because a classical explanation was possible: as it is shown in Fig. 6 the
optical spectra is the same is spin is ignored. Unfortunately is not so easy to produce because obtain
magnetic fields stronger than one Tesla in the lab conditions is not so easy.
Anomalous Zeeman effect

Now the field is weaker than one Tesla an Fine structure has to be taken into account. The change in
energy levels is
∆Enjmj ,ls = < njmj , ls|H 0 |njmj , ls >= µB B (mj + < njmj , ls|sz |njmj , ls >) = mj gµB B
j(j + 1) + s(s + 1) − l(l + 1)
g = 1+ (6.29)
2j(j + 1)

where g is the Landé factor. In order to get < sz > the identity [J 2 [J 2 , s]] = 2 J 2 s + sJ 2 −
4 (s · J) J and (and alternative calculation can be done by using the Wigner-Eckart theorem, as well
as the Chlebsh-Gordan coefficients)
m
< sz >= [j(j + 1) + s(s + 1) − l(l + 1)] (6.30)
2j(j + 1)
Fig. 7 shows the resulting spectra in this case for the n = 2 → n = 1 in a hydrogenic atom. Notice
the complexity of the resulting spectra an how spin is needed to understand it. Historically when this
effect was analyzed theoretically spin was not known and no explanation was obtained, therefore the
name Anomalous Zeeman effect.
6.2. HYDROGENIC ATOMS IN EXTERNAL FIELDS 177
6.2.2 Paschen-Back effect

It is obtained when the magnetic field is no as strong as in the former case and the Fine structure
begins to be important (see Fig. 8). The Lorentz triplet begins to suffer an additional splittins.
6.2.3 Stark effect

It was discovered by J. Stark and A. Lo Surdo in 1913. In this case the atom is in presence of an
external electric field E and the Hamiltonian is
H 0 = eE · x (6.31)
The effect is called strong if the splitting produced is larger than the Fine Structure (eE >>
10−5 eV/a0 ∼ 0.1 MeV/m). This is the typical case given than usual fields are of the order eE ∼ 10
MeV/m. On the contrary the effect is weak if the electrical field is eE << 0.1 MeV/m For the Strong
Electric field, where Fine Structure is negligible
∆Enlm = eE < nlm|z|nlm >= (−1)l (−1)eE < nlm|z|nlm > (6.32)
and vanish if l is even, like i nthe case of the s-states. In the case of the level n = 2 for hydrogenic
atoms the matriz (for the degenerate states 2s and 2pm)
 
0 H12 0 0
 H12 0 0 0 
H 0 = eE 
 0
 (6.33)
0 0 0 
0 0 0 0
R
has to be diagonalized. The matriz element H12 = eE < 2s|z|2p0 >= eE ψ2s zψ2p0 d3 x =
−3eEa0 /Z. The eigenvalue equation is (∆E)2 (∆E)2 − H12 2 = 0, and the solutions are : two degen-
erate states with ∆E = 0 and two with energy shifts ∆E = ±H12 : The two states with m = 0 become
mixed and shifted. See Fig. 9
∆E = 0, ψ2p,m±1
√
∆E = ±3eEa0 /Z, ψ± = (ψ2 s ± ψ2p0 )/ 2 (6.34)
Notice that parity and L2 are not conserved anymore as they do not conmute with H 0 . The z-
component of the angular momenta is still conserved because the ssytem is symmetric under rotations
around the z-axis, the electric field.
An interesting effect due to Stark effect is the dramatic change of the 2s lifetime: normaly, in the
vacuum its lifetime is τ2s ' (1/7) sec. !. However if an external electric field is present the lifetine
change to a typical atomic valued of τ ' 1.3 · 10−12 sec.! (for a field of eE ' 10 MeV/m). The change
is due to the fact than the new field introduces a mixing of the 2s state with the 2p0 one. The second
one is allowed to decay normally (in the electric dipole appoximation, to be addressed in the next
chapter) to the ground state 1s, while the 2s is not.
Given that in many case the predicted correction vanish at first order it is important to go to next
order. For the case of 1s, for example one has (Bransden ?)
(2)
X | < nlm|z|1s > |2 a30 2
∆E1s = (eE)2 = −2(4π0 ) E (6.35)
(0)
E1 − En
(0) Z4
n=±1,lm
as we can see the effect is very small and depends of the square of the electric field this is wy is
called the Quadratic Stark effect.
Finally let us mention another effect su to the precense of an external electric field: it is the atomic
ionization predicted by J. Oppenheimer in 1928. As it is shown in the fig. the nuclear coulombic field
is modified by the precense of the external electric field. The resulting potential energy shows a ‘bag’
arouns the nucleai but as one can see the confined electron can scape by penetrating the barrier, the
tunnel effect. Thus the atom become ionized.
6.3 Several electrons atoms

6.3.1 Helium
In this case the Hamiltonian is

1 1 1 α
H=− ∇21 + ∇22 − Zα + + (6.36)
2m r1 r2 |r1 − r2 |
One can estimate the energy of the ground state, by neglecting the electrostatic repulsion. in
this case the two electrons can be acomodated in the hydrogenlike 1s state: 1s1s = (1s)2 and
E0 = −2(m/2)(Zα/1)2 = −m(Zα)2 = −108.8 eV. Taking into account the electrostatic repulsion,
perturbatively it is obtained that
Z
|ψ1s |2
E0 = −m(Zα)2 + α d3 x1 d3 x2
|r1 − r2 |

5Z 5
= −m(Zα) +2
mα = −Z Z −
2
mα2 = −74.8 eV (6.37)
8 8
It can, still improved by using the variational principle of the former chapter. A simple physical choice
is the wavefunction
(mZ 0 α)3 −mZ 0 α(r1 +r2 )
ψ(r1 , r2 ) = e (6.38)
π
been Z 0 the variational parameter. The result is obtained to be

0 2 5 0 0 5 2
E0 = −mα 2
(Z ) − 2ZZ + Z = −mα Z −
2
= −77.5 eV (6.39)
8 16
where Z 0 = Z − 5/16 < Z was obtained from the minimization of the energy. The experimental
value is E0exp. = −78.975 eV, so the discrepancy is around 2%. The ionization energy, the energy needed
to remove one electron can be obtained to be E0ion. = −m(Zα)2 /2 − E0 = −54.4 − (−78.975) = 24.6
eV.
6.3. SEVERAL ELECTRONS ATOMS 179
More elaborate methods produce high precision results like the ionization energy, compared with
the experimental result
I theo. = 198 310.699 (50) cm−1 , I exp. = 198 310.82 (15) cm−1 (6.40)
Z Enopert. Epert. Evari. Eaccu. Itheo. Iexp.

1 H− −27.2 -10.2 -12.9 -14.368 0.754212 0.75(1)
2 He −108.9 -74.8 -77.5 -79.023 24.5875449 24.58756(2)
3 Li+ -244.9 -193.9 -196.5 -198.10 75.6406998 75.6406(3)
4 Be2+ -435.4 -367.4 -370.1 -371.7 153.8975 153.89(1)
5 B3+ -680.3 -595.4 -597.8 -599.473 259.3769 259.37(2)
6 C4+ -979.6 -877.6 -880.3 -881.939 392.0951 392.09(4)
Table: Ground state energies (in eV) for two electron atoms. Bransden, QM 490 and AM 270, 279.
exp.
Eion. in Flügge II, 61-65 tables. Frankowski, Pekerrs Schwatz (?).
Exited states energies can be estimated by neglecting the electrostatic repulsion: are the states
1s2l, with l = 0, 1, thus E1 = −(5/2)mα2 = −28.03 eV. It can improved by taking into account the
electrostatic repulsion, perturbatively. Given that the wavefunction has to be antisymmetric on can
write that
para 1
ψlm = √ [ψ1s (r1 )ψ2l (r2 ) + ψ1s (r2 )ψ2l (r1 )] χ00
l
2
1
ortho
ψlm l ms
= √ [ψ1s (r1 )ψ2l (r2 ) − ψ1s (r2 )ψ2l (r1 )] χ1ms (6.41)
2
for parahelium (singlet, S = s1 + s2 = 0) and orthohelium (triplet, S = 1). Taking the electrostatic
energy as a perturbation one has to diagonalize a 4 × 4 matriz and a 12 × 12 for parahelium and
orthohelium, respectively:
Z Z
d3 r1 d3 r2 d3 r1 d3 r2 ∗ ∗
∆E = α |ψ1s (r1 )|2 |ψ2l (r2 )|2 ± α ψ1s (r1 )ψ2l (r2 )ψ1s (r2 )ψ2l (r1 ) (6.42)
r12 r12
for the singlet and the triplet, respectively. It is found that the 1s2p state is above the 1s2s one. See
Eisbeg and Flügge II 61.
Lithium is treated in Flügge II 69.
6.3.2 Several electrons atoms

The Hamiltonian in this case is (the CM motian is taken into account in Bransden and Park):
N
X N
X
−1 Zα α
H= ∇2i − + (6.43)
2m r rij
i=1 i>j
6.3.3 General Considerations

Pauli Exclusion’s Principle, Slater’s determinant
Softer version: Only one electron can be in each state Stronger version: The electronic wavefunc-
tion has to be totally antisymetric under the interchange of any pair of electrons. Symmetric and
antisymmetric wavefunction for N particles:
1 X
ψS (1, 2, · · · , N ) = √ ψα (1)ψβ (2) · · · ψω (N ) (6.44)
N! P
For the symmetric case. The numbers 1,2,3, etc are the generic coordinates of the particles 1,2,3,
P
etc. The letters are the quantum numbers needed to characterize the corresponding states. P
means sum over all the permutations of two electrons. For the antisymmetric case one has the Slater
determinant

ψα (1) ψα (2) ··· ψα (N )

1 ψβ (1) ψβ (2) ··· ψβ (N )

ψA (1, 2, · · · , N ) = √ .. .. .. .. (6.45)
N ! . . . .

ψω (1) ψω (2) ··· ψω (N )
For example for the case of two electrons one obtains
1
ψA (r1 , r2 ) = √ [ψα (r1 )ψβ (r2 ) − ψα (r2 )ψβ (r1 )] triplet
2
1
ψS (r1 , r2 ) = √ [ψα (r1 )ψβ (r2 ) + ψα (r2 )ψβ (r1 )] singlet (6.46)
2
One has to remember that the wavefunction of Bosons (those with integer spin, like photons, pions,
etc.) has to be symmetric while it has to be antisymmetric for fermions (those with semi-integer spin),
like electrons, protons, etc. In particular for our case here the total wavefunction of the electrons has
to be antisymmetric. One has to remember that the total wavefunction has to take into account the
spin of the electron, so
ψ(1) = ψ(r1 , t)χ(s1 ) (6.47)
Exchange Forces
Let’s consider the case of two electrons: one has a triplet with spin one and a singlet with spin zero.
In the first case the spin wavefunction is symmetric, while in the second is antisymmetric. Due to
the fact that the total electrons wavefunction must be antisymmetric one sees that in the first case
the space wavefunction has to be antisymmetric and for the second it has to be symmetric from eq.
(6.46):
Now one see that for the triplet case if r1 ∼ r2 then ψA (r1 , r2 ) ∼ 0 and the probability of have the
two electrons close to each other is almost zero like if there would be a repulsion force (the ‘interchange
6.3. SEVERAL ELECTRONS ATOMS 181
force’). In this case the contribution to the energy due to√the electrostatic repulsion between them
is low. For the singlet case if r1 ∼ r2 then ψA (r1 , r2 ) ∼ 2ψα (r1 )ψβ (r1 ) 6= 0, so this configuration
is energetically favored and the ‘interchange force’ is attractive. See fig. 9-7 of Eisberg, about the
importance of the ‘Exchange forces’
6.3.4 Central Potentials, Self Consistent Aproaches

The hamiltonian for this case is (neglecting electron spins, etc.)
N
X N
X N
X N
X
−1 Zα α
H = ∇2i − + + Vc (ri ) − Vc (ri ) = Hc + HI
2m ri rij
i=1 i>j i=1 i=1
N
X N
X N
X
−1 2 α Zα
Hc = ∇i + Vc (ri ) , HI = − + Vc (ri ) (6.48)
2m rij ri
i=1 i>j i
Where the term corresponding to the central potential has been added. The idea is to choose this
potential as some kind of average one, acting on one electron due to the presence of the rest of the
electrons. Thus one solve the first hamiltonian, for one electron!. Once have the energy levels fill
the states in ascending order, taking the electrons as free ones (no interaction). The method can be
improved by taking HI as a perturbation (small one) and correcting the former energies. The point
is how to chose the central potential. Two possibilities are given below
Thomas-Fermi
It was proposed the Thomas and Fermi in 1928 and it should work in the case of large atomic numbers.
The total number of electrons is (taking into account the spin of the electron) at T = 0
Z Ef
(2mEf )3/2 V (2m)3/2 V 1/2
N= 2N (E)dE = with N (E)dE = E dE (6.49)
0 3π 2 2π 2
so Ef = (2π 2 N/V )2/3 /2m. Now Ef = −V (r) (all levels filled?, Virial, Bransden AM 313) so
(−2mV (r))3/2
N/V = (6.50)
3π 2
Selfconsistency means that Gauss Law has to be satisfied:
∇2 φ = −ρ/0 (6.51)
where V (r) = −eφ and ρ = −eN/V . So φ(r) has to satisfy the equation (selfconsistency)
1 d2 4α
rV (r) = − [−2mV (r)]3/2 (6.52)
r dr 2 3π
Redefining r ≡ bx, b = (3π)2/3 /27/3 mαZ 1/3 = 0.8853/mαZ 1/3 and V = −Zα · χ(r)/r one has
d2 χ(r) 1
= 1/2 χ3/2 (6.53)
dx 2 x
with the boundary conditions
(
−Zα/r for r → 0
V (r) →
−(Z − N + 1)α/r for r → ∞
(
1 for x → 0
χ(r) → (6.54)
(Z − N )/Z + 1/Z ' 0 for x → ∞
Having χ one has V to solve the Schrödinger equation. Once the energy eigenvalues are obtains
the electrons can be placed in such way that the Pauli’s exclusion principle is obeyed. It is noticeable
that it works also for atoms with small atomic number
Hartree-Fock
Initially developed by Douglas and Hartree in 1928, however the first computer calculation was done
by the first time by Herman and Skillman in the 60-s. The idea is that each electron moves under
the influence of a central potential V (r) produced by the nuclei and the average motion of the other
electrons, that has to satisfy asymptotic conditions given in eq. (6.54). On can find an initial guess for
the potential satisfying asymptotic conditions. Then solve the Schrödinger Equation for one electron
to find the wavefunction and the charge density ρ = −e|ψ|2 and from it the electric potential φ, by
solving the Poisson eq. (6.51) (Eisberg, Limusa).
Z X
1
ρ(r) = ρ(rk ) = dΩ |ψi (r)|2 (6.55)
4πr2
i6=k
Given that the potential is related to the electric potential by V = −eφ one have the new potential
to solve the Schrödinger equation and make the following iteration. This procedure is continued until
the potential, wavefunction, etc do not change anymore, that is the Schrödinger and Poisson equations
are self-consistent.
The energy levels obtained are ordered like
1s, 2s, 2p, 3s, 3p, [4s, 3d], 4p, [5s, 5d], 5p, [6s, 4f, 5d], · · · (6.56)
where the order of the levels in squared parenthesis may change.
6.3.5 Periodic Table

The electronic configuration. For hydrogen 1 H: 1s1 , for helium 2 He: 1s2 , for Lithium 3 Li: 1s1 2s1 and
for Beryllium 4 Be: 1s2 2s2 . see Fig. 9.14 Eisberg.
6.4. MOLECULES 183
6.3.6 LS and JJ couplings

When Fine Structure is important one has to correct the hamiltonian like
N
1 X 1 dV (ri )
H → H + Hso , Hso = L·S (6.57)
2m2 ri dri
i=1
If |H1 | >> |H2 | (like for small and intermediate values of Z) one has to use the so called LS
coupling case, while for |H1 | << |H2 | (like for large values of Z) one has to use the so called JJ
coupling case. When they are comparble is the intermediate case.
6.3.7 X rays
6.3.8 External Fields
Stark and Zeeman effects.
6.4 Molecules
6.4.1 Born-Oppenheimer
Hydrogen molecule, Morse Potential
6.4.2 Electronic Spectra

6.4.3 Roto-vibrational spectra
Raman Spectra
6.4.4 Van der Walls forces

6.5 Exercises on Atomic Physics

6.5.1 Reduced Mass
6.5.2 General, Breit Fermi
1. For the case m2 > m1 |njmj , lj1 s1 s2 > obtain [H, L2 ], [H, J12 ], [H, J], [J, f (r)] = 0 for
J1 = L + s1 . One has the operators L · s1 , L · s2 , s1 · s2 , s1 · xs2 · x
One has for L:
[Li , xj ] = iijk xk , [Li , pj ] = iijk pk , [Li , x2 ] = [Li , p2 ] = [Li , f (r)] = [Li , f (|p|)] = 0 (6.58)
[Li , L · s1, 2 ] = iijk Lj (s1, 2 )k , [Li , s1 · s2 ] = 0, [Li , x · s1 x · s2 ] = iijk [x · s1 (s2 )j + x · s2 (s1 )j ] xk
For L2
[L2 , L · s1, 2 ] = [L2 , s1 · s2 ] = [L2 , x2 ] = 0,

[L2 , xa xb ] = 2i [iak xb + ibk xa ] xk Li + 6xa xb − 2δab x2 (6.59)
For s1 :
[s1i , L · s1 ] = iijk Lj s1k , [s1i , L · s2 ] = 0, [s1i , s1 · s2 ] = iijk s2j s1k

[s1i , x · s1 x · s2 ] = iijk xj s1k x · s2 (6.60)
For J1
[J1i , L · s1 ] = 0, [J1i , L · s2 ] = iijk Lk s2j , [J1i , s1 · s2 ] = iijk s1k s2j

[J1i , x · s1 x · s2 ] = iijk x · s1 s2j xk (6.61)
For J21
[J12 , L · s1 ] = 0, [J12 , L · s2 ] = 2iijk s1i s2j Lk , [J12 , s1 · s2 ] = 2iijk Li s1k s2j

[J12 , x · s1 x · s2 ] = 2iijk x · s1 s2j xk J1i + 2x · s1 x · s2 (6.62)
and finally J = L + s1 + s2 , and J 2 commute with all four operators.
2. For the case m2 = m1 obtain [H, L2 ], [H, S 2 ], [H, J]. The operators L · S, s1 · s2 and T .
|njmj , lss1 s2 >
3. Vi is called a vector with respect to J operator if it satisfied the commutation relations Vi ,

[Ji , Vj ] = iijk Vk . Show that for any vector operator (Bransden AM 216)
6.5. EXERCISES ON ATOMIC PHYSICS 185
(a) [J 2 , Vi ] = 2Vi + 2iijk Vj Jk
[J 2 , Vi ] = ijik (Jj Vk + Vk Jj ) = ijik (2Vk Jj + ijkl Vl ) = 2Vi + 2iijk Vj Jk (6.63)

(b) [J 2 , [J 2 , Vi ]] = 2 J 2 Vi + Vi J 2 − 4Ji V · J,

[J 2 , [J 2 , Vi ]] = 2 J 2 , Vi + 2iijk J 2 , Vj Jk = 2 J 2 , Vi + 4iijk Vj Jk + 4 Vi J 2 − Vk Ji Jk

= 2 J 2 , Vi + 4 (iijk Vj − Vk Ji ) Jk = 2 J 2 , Vi − 4Ji (V · J) (6.64)
(c) < V >= h(V · J) Ji /j(j + 1) and

(d) Show the last relation by using the Wigner-Eckart theorem.
4. Show that a) x, b) p c) L, d) s and e) (s · x) x are vector with respect to J = L + s
a) [Li , xj ] = [Ji , xj ] = iijk xk

b) [Li , pj ] = iijk pk
c) [Ji , Lj ] = [Li + si , Lj ] = [Li , Lj ] = iijk Lk
d) [Ji , sj ] = [Li + si , sj ] = [si , sj ] = iijk sk
e) [Ji , (s · x) xj ] = [Li + si , (s · x) xj ] = [Li , (s · x) xj ] + [si , (s · r) xj ]
= (s · r) [Li , xj ] + sl [Li , xl ]xj + [si , sl ]xl xj = (s · r) iijk xk + sl iilk xk xj + iilk sk xl xj
= iijk (s · r) xk + iikl sk xl xj + iilk sk xl xj = iijk (s · r) xk (6.65)
5. For G = L − s + 3s · rr/r2 and J = L + s show that
(a) is a vectorial operator: it satisfied [Ji , Gj ] = iijk Gk

Given the former item and the linearity of the commutator it is clear G is an operator
(b) Show that G0 · J = s · L for G0 = s − 3 (r̂ · s) ŝ and J = L + s
A: One has that
G0 · J = s2 − 3 (r̂ · s)2 + s · L − 3 (s · r̂) r̂ · L = s · L (6.66)
Given that for a spin s = 1/2 particles s2 = 3 (r̂ · s)2 , for the properties of the Pauli matrices
and r̂ · L = 0 for the definition of L .
6. Obtain < lm|r̂i r̂j |l0 m0 > where r̂ = r/r (Gershtein, hep-ph/9504319, Kwong and Rosner, Phys.
Rev. D38, 279, Landau III in nuclear hyperfine structure, Eichten and Quigg, PR D49, 5845
(1994)).
A: < lm|r̂i r̂j |l0 m0 >= a(Li Lj + Lj Li )mm0 + bδij δmm0 . Given that a) r̂i r̂i = 1, b) r̂i Lj = 0 and c)
the conmutation relations for L one obtains a and b, so
1
< lm|r̂i r̂j |l0 m0 >= − (Li Lj + Lj Li )mm0 − (2L2 − 1)δij δmm0 (6.67)
4L2 −3
7. Obtain < lm|6 [r̂i r̂j − δij /3] si1 sj2 |l0 m0 > where r̂ = r/r
A: Given that s = s1 + s2 , s · r̂ = s1 · r̂ + s2 · r̂, taking their squares and using the fact that
[si · r̂]2 = s2i and si1 sj2 + sj1 si2 = δij /2 one obtains that [r̂i r̂j − δij /3] si1 sj2 = [r̂i r̂j − δij /3] si sj /2.
Thus, using the commutation relations for s and L (BS 348, 109)
1
< lm|6 [r̂i r̂j − δij /3] si1 sj2 |l0 m0 >= − 6 < L · S >2 +3 < L · S > −2L2 S2 (6.68)
4L2−3
6.5.3 Fine Structure
8. Is it possible to have the ‘Fine structure’ for multielectron atoms?, why?, for positronium?
9. problem 4-10, Eisberg and Resnick, p. 117.
10. Historically, was the spin hypothesist necessary to explain the Fine Structure?
A: No, Sommerfeld did it in 1919 without involving spin.
11. Obtain the term H10 , corresponding to the relativistic kinetic energy is two particles
A:
p p2 p4
K= m2 + p2 − m = − + ··· (6.69)
2m 8m3
and one obtains H10 for two particles.
12. Show the H20 is diagonal, in the base |J, mJ ; l, s >.
13. Obtain the hamiltonian for the ‘Spin-orbit’ interaction H20 = (Zα/2m2 )L · s/r3 . What is the
physics behind the ‘Spin-orbit’ interaction?
14. Expand the Dirac formula for the energy states to obtain the nonrelativistic formula.
15. Work out the transition from n = 2 to n = 1: spectra and widths, for the case of ‘Fine structure’.
16. Find the energy change in the hydrogenoic atom levels due to the Darwin’s tem:
πZα (3)
H0 = δ (r)
2m2
Sketch the new levels.
17. Find the energetic and optical spectra for the lines n = 2 and n = 1, for the ‘Fine Structure.
Workout the numerical values for hydrogen and for Z = 92.
A:
2
∆Enj Zα 3 n
=− − (6.70)
En n 4 j + 1/2
and ∆Enj /En = 1.3 · 10−5 for hydrogen and ∆Enj /En = 0.11 for U 92 .
18. What happens to the lines Hα and Hβ when it is possible to measure the ‘Fine structure’ ?: Find
the energetic and optical spectra. Workout the numerical values for hydrogen and for Z = 92.
Considering the Doppler broadening of the lines and without it? and the natural width of each
of the Hα lines (see radiation chapter) and T = 300 o K.
6.5.4 Lamb-Retherford
19. The contribution of the vacuum polarization to the Lamb shift is (Itzykson 328, Bjorken 158)
4 α(Zα)4
∆Enl = − mδnl ' −27 MeV (6.71)
15π n3
Dirac = 132 279.96 eV [ref 9], E exp. = 131 812 eV. U 91+ . ν = 468(13) eV.
20. Lamb-Retherford E1s 1s
PNU #506.T. Stoeklker, et al., Phys. Rev. Lett. 85, 3109 (2000) (good rev.). Lyman-alpha
(n = 2 → n = 1).
A: A:
∆Enjl α (Zα)2
=− k(n, l) (6.72)
En 2 n
and for the ground state (n = 1, l = 0) ∆Enj /En = −2.5·10−6 for hydrogen and ∆Enj /En = 0.02
for U 92 .
21. For positronium find the energetic and optical spectra in the approximations: a) Schrödinger,
b) Fine structure, c) Lamb-Retherford.
22. About the Lamb-Retherford Schiff find its: history, the physics, size, etc. Is it possible to have
the Lamb-Retherford swift for multielectron atoms?, why?, for positronium?
6.5.5 Hyperfine structure
23. Obtain the hyperfine lagrangian, taking into account the magnetic field produced by the nuclear
magnetic momenta and its interaction with the orbital momenta and with the electron magnetic
momenta
A: A magnetic dipole momenta produces the vectorial and a magnetic field (obtained with the
help of the last two identities)

−µ0 1 µ0 µN × r
A = µN × ∇ =
4π r 4π r3

µ0 (µN · r)r
B = ∇×A= 3 − µ N + µ0 µN δ (r)
(3)
4πr3 r2
∇ ∧ (A ∧ B) = (∇ · B) A − (∇ · A) B + (B · ∇) A − (A · ∇) B

1 1 4 (3) 3ri rj
∇i ∇j = − 3 + πδ (r) δij + 5 (6.73)
r r 3 r
There are two contributions to the energy (see Fig. 3): the nuclear ‘spin-orbit’ and the ‘spin-spin’
ie
Hh.f. = Hs−l + Hss = − A · ∇ − µe · B
m
αgN L · sN 1 8π
= − 3 [sN · se − 3(sN · r̂)(se · r̂)] + sN · se δ (r)
(3)
(6.74)
2me mp r3 r 3
the hyperfine hamiltonian used before.
24. Obtain the hyperfine energy correction for l = 0

A: Since the electron has no orbital angular momentum, there is no nuclear spin-orbit effect. It
can be shown that because the wavefunction has spherical symmetry, only the delta function
term contributes from the spin-spin Hamiltonian. First order perturbation theory yields

4πgp α 2 4gN me Zα2 3
∆Ehf
l=0
= (sN · se ) |ψ(r = 0)| = − En f (f + 1) − (6.75)
3mmp 3mp n 2
where sN · se was obtained from F 2 = s2e + s2N + 2sN · se .
25. What is the physical meaning of the hyperfine structure?
26. Sketch what happens for the energetic spectra for the level n = 2 when the experimental reso-
lution increases to measure: the fine structure, the Lamb-Retherford, the Lamb-Retherford and
the hyperfine structure.
27. Find the frequency emitted when positronium makes the transition between the first two energy
levels, considering the hyperfine structure.
28. Find the frequency emitted when hydrogen makes the transition between the first two energy
levels, considering the hyperfine structure.
29. Find the frequency emitted when U91 (Uranium atoms with only one electron!) makes the
transition between the first two energy levels, considering the hyperfine structure.
30. Obtain the energy levels and the wavefunctions for a hydrogenic nuclei with sN = 1 at the level
n = 1.
31. Obtain the energy levels and the wavefunctions for the ground state for a hydrogenic nuclei with
sN = 1/2, Z = 92, A = 238, gI = 2.
A:
∆Enj gN me Zα2 f (f + 1) − sN (sN + 1) − j(j + 1)

=− = −2gN (me /mN )Zα2 (6.76)
En 2mp n j(j + 1)(l + 1/2)
and ∆Enj /En = 1.1 · 10−7 for hydrogen and ∆Enj /En = 4 · 10−8 for U 92 . And ν theo. = 1391 hz
and ν exp. = 1420 hz
6.5.6 Zeeman and Stark effects
32. Show that < sz >= m[j(j + 1) + s(s + 1) − l(l + 1)]/2j(j + 1) by using the Wigner-Eckart theorem
and the Clebsh-Gordan coefficients.
A:
X jmj 2 mj j(j + 1) − l(l + 1) − s(s + 1)
< sz > = < jmj , ls|sz |jmj , ls >= Clml ,sms ms = ± = mj
mm
2l + 1 2j(j + 1)
l s
X jm
|jmj , ls > = Clmlj,sms |lml > |sms > (6.77)
ml ms
for j = l ± 1/2 and given that
1/2 1/2
l+1/2,mj l ± mj + 1/2 l−1/2,mj l ∓ mj + 1/2
Clml ,1/2 = , Clml ,1/2 =∓ (6.78)
±1/2 2l + 1 ±1/2 2l + 1
33. What happens to the line Hα in the case of the ‘Normal’ Zeeman effect?. Find the energetic
spectra and the optical one.
34. Describe the Normal, the anomalous effects.
35. What is the Pashen-Bach effect
36. Sketch the spectra for the Anomalous Zeeman effect for the line 2d3/2 − 1s1/2
37. Sketch the spectra for the Anomalous Zeeman effect for the line 3d5/2 − 2p3/2
38. Sketch the spectra for the Anomalous Zeeman effect for the line 2d3/2 − 1s1/2 .
39. Obtain the energetic splitting for a level n = 2 when it is exposed to a magnetic field of a)
B = 10 T and b) B = 0.5 · 10−4 T.
A: They are, respectively Normal and anomalous Zeeman effects.
40. What happens to the lines Hα and Hβ line due to the ‘Normal’ Zeeman effect?.
41. Is the angular momenta l a good quantum number when external electrical fields are present?
42. Is the angular momenta projection along a constant electric field, m a good quantum number
when external electrical field is present?.
43. For the Stark effect of the line n = 3, what is the dimension of the matrix one has to diagonalize.
Which matrix elements vanish?
44. Is it possible to ionize an atom by exposing it to a electric (gravitational) field?

A: Yes, due to the tunnel effect.
45. Briefly, what is the Hartree-Fock approximation?.

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Chapter 7
Radiation
7.1 Semiclassical radiation theory

The Semiclassical theory of radiation was introduced immediately the formulation of QM around
1926. In this formalism particles are quantized although nonrelativistic while EM fields are classical.
Classical Fields can be obtained from the potentials (scalar and vector ones):
∂
E = −∇φ − A, B = ∇ ∧ A (7.1)
∂t
A monochromatic wave can be described as
A = A0 cos(k · x − ωt), E = −ωA0 sin(k · x − ωt)), B = −A0 k ∧ sin(k · x − ωt) (7.2)
with φ = 0, ∇ · A = 0 so k · = 0 (in the gauge of Coulomb, radiation or transverse). For this

case the energy density and the energy flux, or the Poynting vector are
0 0
= < E 2 > + = ω 2 A20 = nω
2 2
0 2 2
< S >= 0 < E ∧ B >, | < S > | = ω A0 = nω (7.3)
2
with n the space photon density.
Particles are treated by the SE and the interaction withe the radiation can be taken into account
by the so called ‘minimal substitution’ or gauge invariance:
1 1 e
H = (p − eA)2 + eφ = p2 + e2 A2 − ep · A − eA · p + eφ = H0 − A · p
2m 2m m
e p2 e
H0 = − A·p+ '− A·p (7.4)
m 2m m
where the Coulomb gauge was chosen, H0 = p2 /2m + eφ, the quadratic term was assumed to be
negligible for normal fields. The interaction in then characterized by H 0 . Given an atomic system
interacting with radiation the wavefunction is, according to the time perturbation theory
195
196 CHAPTER 7. RADIATION
X X
0 iωnk t
ψ(t) = an (t)eiEn t ψ (0) (t), i · an = Hnk e ak
n k
0 0 eA0
Hnk = < n|H |k >= − < n| cos (k · x − ωt) · p|k > (7.5)
m
7.1.1 Multipolar expansion, Electric and magnetic dipole approximations

The spatial dependence inside the expecting value, can be expanded in terms of the ratio aB /λ for
radiation even in the ultraviolet range. For example for the optical range (λ = 4000 − 7000 Å) and
aB /λ = 4.5 − 7.8 · 10−4 . The expansion is
1
ek·x = 1 + ik · x + (ik · x)2 + · · · (7.6)
2!
and replacing in eq. (7.5) the terms cof the expansion correspond to electric dipole, magnetic
dipole, quadrupole, etc. At first order, in the electric dipole approximation
0 eA0
Hnk =− cos(ωt) < n| · p|k >= −ieA0 cos(ωt) < n| · [H0 , x]|k >= −ieA0 ωnk cos(ωt) · xnk (7.7)
m
where the relation p = im[H0 , x] = im[p2 /2m + V, x] was used and ωnk = En − Ek . Thus the
equations to be solved are
X
ȧn = −eA0 cos (ωt) ωnk · xnk ak (7.8)
k
Now one can take the ‘two state’ approximation, given that only the frecuency close to ω ' ωnk
gets exited, while the other proper frecuencies do not participate. In this approximation
(0)
ȧa = c cos (ωt) e−iω0 t ab ' c cos (ωt) e−iω0 t ab
ȧb = −c cos (ωt) eiω0 t aa ' −c cos (ωt) eiω0 t a(0)
a (7.9)
7.1.2 Absorsion of Radiation

In this case the initial conditios are
(0)
ab (T ) = 0, a(0)
a (T ) = 1
Z t
(0) c
ab (t) = − eiωt + e−iωt eiω0 t dt (7.10)
2 −T
with c = eA0 ω0 · xnk and the probalility for the transition from a to b is
7.1. SEMICLASSICAL RADIATION THEORY 197
Z
(0) |c|2 t iω0 t 2
P (a → b) = |ab (t)|2 = e +e
iωt −iωt
e dt
4 −T
Z t Z t
|c|2 −iωt
iω0 t
' e +e
iωt
e dt eiωt + e−iωt e−iω0 t dt
4 −T −T
Z t Z t Z t
|c|2 −iωt
−iω0 t π|c|2 −2iω0 t
' [2πδ(ω − ω0 ) + 0] e +e
iωt
e dt ' δ(ω − ω0 ) dt + e dt
4 −T 2 −T −T
π|c|2
' δ(ω − ω0 )(t + T )
2
P (a → b) π|c|2
R(a → b) ≡ = δ(ω − ω0 ) = 4π 2 αu| · xnk |2 δ(ω − ω0 ) (7.11)
t+T 2
the ratio of absortion: the probability of transition by unit of time, for a given frecuency and po-
larization. Notice the dirac’s delta mantaining the energy conservation. Given that not all frecuencies
are absorved
∆R = 4π 2 α∆u| · xnk |2 δ(ω − ω0 ) = 4π 2 αI(ω)| · xnk |2 δ(ω − ω0 )∆ω

Z
∆R = 4π 2 α dωI(ω)| · xnk |2 δ(ω − ω0 )dω = 4π 2 αI(ω0 )| · xnk |2 (7.12)
where the incident flux I = ∆u/∆ω. The absortion differential cross section
∆R dΩ dσ
dσ = , = πα| · xnk |2
I 4π dΩ
Z 1
1 2 4π 2
σ̄ = πα|xnk |2
sin θ + 0 · 2πd cos θ = α|xnk |2 (7.13)
−1 2 3
for totally unpolaraized light
7.1.3 Estimulated emision

Now the initial conditios are
(0)
ab (T ) = 1, a(0)
a (T ) = 0
Z t
c
a (t) =
a(0) eiωt + e−iωt eiω0 t dt (7.14)
2 −T
sot the result is the same, interchanging the initial and final states. The result is the same and
one obtain the ‘Detailed balance principle’ (also abtained fron Time reversal symmety):
R(b → a) = R(a → b) (7.15)
for each pair of initial and final states

7.1.4 Spontaneous emision

In this case emision is possible even in the absense of external fields. As we have seen, according to
the semiclassical theory of radiation.
R(a → b) ≡ Rind. (b → a) = 4π 2 αu| · xnk |2 δ(ω − ω0 ) (7.16)

As we can see spontaneous emision is not possible!. In the Quantum Field Theory (QFT) one has
to reinterpret the energy density as u = nω = (N/V )ω: the numeber of photons of energy ω in a given
volume V . The result in this case is [23]
N
ωba | · xba |2 δ(ω − ω0 )
Rabs. (a → b) = 4π 2 α
V
N +1
Remi. (b → a) = 4π 2 α ωba | · xba |2 δ(ω − ω0 ) (7.17)
V
where in the second case estimulated and spontaneous cases are included, thus QFT solves this
problem. For spontaneous mition no photons sorround the atom and N = 0. In order to obtain the
total rate of transition we have to sum over the possible final states: d3 n = V d3 k/(2π)3 , where k is
the photon momenta:
α α V ωdω dΩ
dΓspo. = Rspo. d3 n = 4π 2 ωba | · xba |2 δ(ω − ω0 )d3 n = 4π 2 ωba | · xba |2 δ(ω − ω0 )
V V (2π)3
dΓspo. α 3 4α 3 1 X
= ωba | · xba |2 , Γspo. = ωba |xba |2 , Γ̄spo. = Γ(b → a) (7.18)
dΩ 2π 3 gb
a, b
the angular distribution for a given photon polarization, initial (final) state b (a). The second
equation is obtained by integrating over all the possible directions and adding the two possible polar-
izations of the emitted photon. The last one by averaging over the gb (the degeneracy of this level)
initial states b and adding over the possible final ones. Finally the lifetime of a given state is τ = 1/Γ
(adding over all possible final states), given that Ṅ = −N Γ (N is the number of exited atoms at time
t) and
N = N0 e−Γt (7.19)
7.1.5 Black body radiation

7.1.6 Selection rules
Electric dipole selection rules are ∆l = ±1, ∆J = 0, ±1 and the transition J = 0 → J 0 = 0 is
forbidden Bethe-Salpeter 271.
The magnetic dipole selection rules are: ∆l = 0, ∆J = 0, ±1, except the transition from J = 0 to
J 0 = 0 that is forbidden; and ∆mJ = 0, ±1.
For the quadrupole one has the selection rules: ∆l = 0, ±2 (except the transition from l = 0 to
l0 = 0) and ∆m = 0, ±1, ±2.
7.1.7 Half-life and line width. Photoelectric effect

7.2. RADIATION EXERCISES 199
7.2 Radiation exercises

1. Show that the Semiclassical Theory of Radiation is a Gauge Theory: it is invariant under the
transformation, for all function α(x, t)
ψ → exp[iα(x)]ψ, qAµ → qAµ + ∂µ α (7.20)
2. For a diatomic molecule bounded by a potential, that can be approximated by a 1-D harmonic
oscilator compute the lifetime of the first exited state, with ω = 10−13 seg−1 .
3. What is the prediction of the Semiclassical Theory of Radiation for the Spontaneous emition.
4. What is the electric dipole approxiamtion?, why is it valid?
5. Is it the electric dipole approximation valid for microwaves?
6. For what wavelenghts is the electric dipole approximation valid?
7. Show that spontaneous emition radiation formula (eq. (7.18))agrees with Larmor formula (for
a given electric dipole momenta)
A: Larmor formula for radiated power, by a electric dipole driven a frecuency ω is
1 ω 4 d2 4 ω 4 e2 4
P = = = αω 4 x2 = Γω (7.21)
3 4π0 3 4π0 3
8. Complete the ‘Grotrian diagram for a) an spherical infinite well, b) the isotropic harmonic
oscilator, c) positronium and a system whose states are ordered as: 11 s0 , 13 s1 , 21 s0 , 23 p0 , 21 p1 ,
23 p1 , 23 p2 , 23 s1 .
9. Is it or not possible the transition 5d → 1s?, why?.
10. Why the ‘two states approximation’ is valid?
11. Show that Γ(2s → 1s) = 0
12. Compute the lifetime of each of the sublevels of the state n = 2 of a hydrogenic atom.
A: In the dipole appoximation only the transitions 2p → 1s are allowed with
dΓspo. α 3 4α 3 1 X
= ωba | · xba |2 , Γspo. = ωba |xba |2 , Γ̄spo. = Γ(b → a) (7.22)
dΩ 2π 3 gb
a, b
Thus one has to obtain the expectation values for the two states
b b
< 2p, m = ±1|r|1s > = ∓ √ (1, ∓i, 0), < 2p, m = 0|r|1s >= √ (0, 0, 1)
6 3
Z ∞ 5
4! 2
b = drr3 R21 R10 = √ a (7.23)
0 6 3
and
dΓ α 3 b2 1α 3 2
m = ±1, 1 : = ω cos θ, Γ= ω b
dΩ 2π ba 6 9 ba
dΓ α 3 b2 α 3 2
m = ±1, 2 : = ω , Γ= ω b
dΩ 2π ba 6 3 ba
dΓ α 3 b2 4α 3 2
m = 0, 1 : = ω sin θ, Γ= ω b
dΩ 2π ba 3 9 ba
dΓ
m = 0, 2 : = 0, Γ = 0 (7.24)
dΩ
if the atoms are initially polarized and final photon polarization is measured
13. Compute the lifetime of the level n = 2, assuming no initial polarization.
14. Compute the lifetime of the level n = 2, if the atom is initially in the states 2s, 2p1, 2p − 1 y
2p0 with probabilities 0.5, 0, 0.3 y 0.2, respectively.
15. Compute the angular distribution of the radiation when the atom goes from the state |2p, m =
−1 > to the ground state, for each photon polarization.
16. For the transition 3s → 2p obtain dΓ/dΩ and Γ for all the posibilities.
Chapter 8
Scattering Theory
8.1 Introduction
History: Rayleigh, Rutherford, acelerators (atoms, nucleia, particles). Colliding beams. Targets.
Lab-CM
One is looking for a solution to the SE with boundary conditions:

iki ·x iki ·x eikf ·x
ψin = Ae , ψout = A e + f (θ, φ) (8.1)
r
In order to get the cross section one has to obtain the incoming and outgoing fluxes (J =
−(i/2m) [ψ ∗ ∇ψ − (∇ψ)∗ ψ]:
ki |f |2 kf
Jin = |A|2 , Jout = |A|2 2 (8.2)
m r m
and
dσ dPf /dΩdt r2 dPf /dAdt r2 |Jout | kf

≡ = = = |f |2 (8.3)
dΩ dPi /dAdt |Jin | |Jin | ki
and for the elastic case where kf = ki one gas for the differential cross section:
Z Z
dσ dσ
= |f |2 , σ = dΩ = dΩ|f |2 (8.4)
dΩ dΩ
8.2 Integral Schrödinger Equation

One has to solve the SE Hψ = Eψ. In general the hamiltonian can be splitted as H = H0 + V , where
the solution to the equation H0 ψ0 = En ψn is supposed to be known. The inhomogenous solution (for
the general solution one has to add the homogenous part) can be written in general, in terms of the
Green’s functions
201
202 CHAPTER 8. SCATTERING THEORY
Z
ψ(x) = dx0 G(x, x0 )V (v 0 )ψ(x0 ), (H0 − E) G(x, x0 ) = −δ(x − x0 ) (8.5)
This is the Integral SE. The Green’s function can be written as
X ψn (x)ψ ∗ (x0 )
G(x, x0 ) = − n
(8.6)
n
En − E
P
where the completeness relation has to be valid: n ψn (x)ψn∗ (x0 ) = δ(x − x0 ). A particular case is
obtained by choosin H0 = −(1/2m)∇2 , so the solution are the plane waves:
1 ki ·x k2
ψk = e , E k = (8.7)
(2π)3/2 2m
so the Gren’s function in this case becomes
Z Z 02 0 Z ∞
0 −1 d3 k 0 ik0 ·(x−x0 ) −2m k dk dx ik0 rx −2m k 0 dk 0 ik0 r −ik0 r

G(x, x ) = e = e = e − e
(2π)3/2 Ek0 − Ek (2π)2 k0 2 − k2 (2π)2 ir 0 k 0 2 − k 2
Z ∞
−2m k 0 dk 0 ik0 r −2m h ikr i −m ikr
= e = πie = e (8.8)
(2π)2 ir −∞ k 0 2 − k 2 (2π)2 ir 2πr
with r = |x − x0 |. Thus one obtains the Integral SE:
Z
−m exp[ik|x − x0 |]
ψ(x) = dx0 V (x0 )ψ(x0 ) (8.9)
2π |x − x0 |
and given that usually |x0 << |x| one expands |x − x0 | ' |x| − x · x0 /|x| + · · · and
Z
−m ikf ·r 0
ψ(x) = e dx0 e−ikf ·x V (x0 )ψ(x0 ) (8.10)
2πr
8.2.1 Born Aproximation

In the case the potential is weak enought the Integral SE of (8.10) can be solved iteratively. The process
can be initialited by choosing the wavefunction inside the integral equal to the original incident wave:
ψ(x) ' ψinc. = Aeiki ·x

Z
mA ikf ·x 0 0 Af ikf ·x
ψdisp = − e d3 x0 e−iki ·x V (x0 )eiki ·x = e
2πr r
Z
m 0
f (θ, φ) = − d3 x0 e−iq·x V (x0 ) (8.11)
2π
8.2. INTEGRAL SCHRÖDINGER EQUATION 203
with q = ki − kf , the transfered momenta. That give us the so called Fermi’s Golden Rule to
compute f , at leading order. Two important cases are the Yukawa and the Coulomb potentials (a
particular case when β = 0):
Zα −βr
V = e (8.12)
r
Applying Fermi’s golden rule one obtain (with q 2 = 4k 2 sin2 (θ/2), dq = k cos(θ/2) dθ and dΩ =
2πqdq/k 2 )
mZα 4π
f (θ, φ) = −
2π β 2 + q 2

dσ 2mZα 2 (Zα)2
= =
dΩ Ruth. q2 16E 2 sin4 (θ/2)

2mZα 2 k2 4π(Zα)2
σYukawa = π = (8.13)
β k 2 + β 2 /4 E02 1 + 4E 2 /E02
This is the differential Rutherford cross section, that coincides with the result obtained by E.
Rutehrford by using Classical Mechanics!: the two results coincide. Notice that no cross section exixts
for the Coulomb case (σ → ∞), due to the long range of this potential. For the Yukawa case (with
E0 = β 2 /2m) the cross section is finite given than the range 1/β is finite.
8.2.2 Form Factors

As it has been obtained
Z
m 0
f (θ, φ) = − dx0 eiq·x V (x0 ) (8.14)
2π
where the potential feel by the an scattered electron is given as V (x) = −eφ(x), with φ(x) the
electric potential produced by the distributed charge of the target. It obeys the Poisson equation
(4φ = −ρ/0 ), that can be written in terms of its fourier components
Z
ρ(q) d3 q −iq·x
φ(q) = , φ(x) = e φ(q) (8.15)
0 q 2 (2π)3
and similarly for ρ(x). Thus
me ρ(q) mZe2 F (q) 2mZα

f = ≡ = F (q)
2π0 q 2 2π0 q 2 q2
Z
ρ(q) 1
F (q) = = d3 eiq·x φ(x) (8.16)
Ze Ze
where F is the Form Factor and Ze is the total charge of the target. The cross section is, then

dσ dσ
= |F (q)|2 (8.17)
dΩ dΩ Ruth.
An example is the structureless nuclei with ρ = Zeδ (3) (x), so F (q) = 1 and the cross section is the
Rutherford’s one. The form factor is then equal to one for an structureless particle. Naturally in the
case experiments show that the form factor depends on the energy the target, or the incoming particle
or both have structure. Thus the form factor give us a description of the structure of the target.
8.2.3 Range of validity of the Fermi’s Golden Rule
8.3 Partial Waves

8.3.1 Partial waves decomposition
Phase shifts δl
Differential and total cross section, in terms of partial waves.
8.3.2 Calculation of δl
in terms of the potential
8.4 Exact solutions

8.4.1 Hard sphere
8.4.2 soft sphere and Finite well
Efecto Ramsauer
8.4.3 Rutherford case

: Potencial de Coulomb parabolic coordinates
8.5 Resonances
8.5.1 Resonances 1-D
8.5.2 Resonances: case of finite well
Ramsauer effect.
8.5.3 Breit-Wigner parametrization
8.6 Spin effects. Identical particles

Interchange potential
8.7. INELASTICITY 205
8.7 Inelasticity
8.7.1 Optical Theorem
Complex potentials (schift p. 129)
8.8 S-Matrix properties

S-Matriz∗ S. Properties: Unitarity, Analiticity. Dispersion relations. Jost Function. Bounded states.
8.9 Lippman-Schwinger Equation
8.10 Approximate Methods

Semiclasical treatment (Sakurai p. 342)
Coulomb+ modified Coulomb.
8.11 Scattering Exercises

8.11.1 Born’s Approximation Exercises
1. Get the cross section for the perfect sphere, by using Classical Mechanics.
2. Get the Rutherford cross section, by using Classical Mechanics.
3. For the potential (V0 > 0, for the soft sphere. V0 > 0, for the finite depth).
(
V0 , if r < a
V (r) =
0 otherwise.
(a) Get the differential cross section. Sketch it

(b) Get the total cross section.
4. For the potential
exp (−r/a)
V (r) = V0
r
with a ' 1/mπ and V0 ' 1. Plot the total cross section.
5. For the potential
(
mω 2 1, if r < a
V (r) = (r − a)2
2 0, otherwise.
get the differential cross section.
6. For the potential V (x) = Cδ (3) (x − a) compute the differential cross section.
7. Calculate the Differential Cross section for the potential
V (x) = cδ(y)δ(z) [δ(x − a) − δ(x + a)]
8. Calculate the differential Cross Section for the charge density, in the target given by ρ(x) =
e1 δ (3) (x − a) + e2 δ (3) (x + a). Comment the
case e2 = −e1 .
9. Calculate the differential cross section for an alpha particle hitting and hydrogenic atom. Hint:
first compute the Form Factor.
8.11. SCATTERING EXERCISES 207
8.11.2 Partial Wave Phases, Exercises
10. Compute the partial wave δ0 (E → 0) for: a) the finite well (V (r) = −V0 ), b) the ‘soft’ sphere
(V (r) = V0 ).
11. Compute the partial waves δl for the Yukawa potential
exp (−r/a)
V (r) = V0
r
12. Compute the Differential Cross Section for the potential
(
Cr4 , if r < a
V (r) =
0 otherwise.
13. If the differential cross section is expanded as
dσ
= A + BP1 + CP2 + · · ·
dΩ
find the values of the constants A, B, C, as function of the partial waves phases δl
14. What are the advantages and disadvantages of the methods: a) Green’s functions and b) partial
waves.
8.11.3 Exact solutions, Resonances and Inelasticity Exercises
15. Compute, using the Classical Physics the differential and the total cross section for the perfect
sphere.
16. What is a resonance, and what conditions must be satisfied in order to have one?.
17. What are the physical meaning

of the parameters in the Breit-Wigner description of the reso-
nances: Γ2 / (E − mR )2 + Γ2
18. a) What are the physical meaning of the parameters in the Breit-Wigner description of the
resonances:
Γ2
σ= (8.18)
(E − ER )2 + Γ2
b) If the formula above is valid can we be sure to have a resonance?, why?
19. (a) Obtain simple expressions for tan(δl ), with l = 0, 1, 2 for the case of the finite well and the
soft sphere.
(b) Plot tan(δl ) (the first l-s)for the case of the finite well. Do you find resonances?, what is
the reason for their presence?
(c) The same as before but for the case of the soft sphere.
20. Bosqueje las ondas parcial δ0 (E → 0) y δ1 (E → 0) para: a) el pozo de potencial finito, V (r) =
−V0 y b) la esfera semirigida, V (r) = V0 para r < a y V (r) = 0 para r > a
21. What is the Optical Theorem for the Elastic and for the inelastic case?
22. (a) Calcule δl para un pozo de potencial de profundidad −V0

(b) Haga un bosquejo de δl=0 el caso del pozo anterior y de una esfera ‘semirı́gida’.
(c) Halle (dσ/dΩ) |E→0 usando ondas parciales y la aproximacion de Born. Compare.
23. Brevemente:
(a) What is the meaning of differential cross section?, can we use this concept for sound waves?
(b) What is the meaning of a large cross section(diferencial y total)?
24. Calcule las seccion eficaces diferencial y total para los potenciales: V (~x) = cδ (3) (~x − ~a), y para
el caso b) V (~x) = cδ(x − a)δ(y)δ(z).
25. Que es una resonancia?, a que se debe?, como sabemos que tenemos resonancia?.
26. (a) Calcule δl para un pozo de potencial de profundidad −V0

(b) Haga un bosquejo de ésta para el caso del pozo anterior y de una esfera ‘semirı́gida, en el
caso de l = 0.
27. (a) Diga en palabras cuando no se puede usar la aproximación de Born

(b) Cuando es mas util el metodo de ‘Ondas Parciales’ ?, porque?.
28. Calcule la seccion eficaz diferencial para una densidad de carga, en el blanco de ρ(x) = e1 δ (3) (x−
a) + e2 δ (3) (x + a). Comente el caso e2 = −e1 .
Chapter 9
Path or Feynman Integrals
9.1 Definitions
9.1.1 Schrödinger representation
The time evolution of Quantum Mechanics is contained, in the Schrödinger equation
∂ ∂
i |Ψ(t) >= H|Ψ(t) >, ori |q, t >= H|q, t > (9.1)
∂t ∂t
with solution
|q, t >= H|q, t >= e−iHt |q, t = 0 > (9.2)
9.1.2 Spatial and momentum representations

Let’s define the coordinates and momentum eigenvalues and eigenvectors as
q̂|q >= q|q >, p̂|p >= p|p > (9.3)

It is not possible to diagonalize them at the same time given that they have to satisfy the commu-
tation relation [q̂, p̂] = i. Besides they are normalized as
< q|q 0 >= δ(q − q 0 ), < p|p0 >= δ(p − p0 ) (9.4)

and satisfy the completeness relations
Z Z
dq|q >< q| = dp|p >< p| = 1 (9.5)
so the transformation between the two representation is given as
1
< q|p >= √ eipq (9.6)
2π
209
210 CHAPTER 9. PATH OR FEYNMAN INTEGRALS
9.1.3 Path or Feynman integrals

The Path or Feynman, Kernel, Green’s function os Schwinger’s function is defined as
0
K(q 0 , t0 ; q, t) ≡< q 0 , t0 |q, t >=< q 0 |e−iH(t−t ) |q > (9.7)
The interval can be divided in n time intervals = (t − t0 )/n, so (See Fig.)
Z
0 0
K(q , t ; q, t) = dq1 · · · dqn−1 < q 0 , t0 |qn−1 tn−1 > · · · < q 0 , t0 |q1 t1 > (9.8)
And
2
< ql , tl |ql−1 tl−1 > = < ql |e−iH |ql−1 >=< ql |e−ip̂ /2m |ql−1 > e−iV (ql−1 )
Z
2
= dp < ql |e−ip̂ /2m |p >< p|ql−1 > e−iV (ql−1 )
Z r
−iV (ql−1 ) dp −ip2 /2m+ip·ql−1 m iLl
= e e = e (9.9)
2π 2πi
with H = p2 /2m + V and L = p2 /2m − V . Then we have for K
Z m n/2 Z R t0 Z
0 0
K(q 0 , t0 ; q, t) = dq1 · · · dqn−1 ei[Ln−i +···+L0 ] = [dq]ei t Ldt = [dq]eiS(q t ,qt)dt
(9.10)
2πi
in the limit of → 0.
9.1.4 Example: Free particle

This case is simple given that L = m · q 2 /2, so
Z R t0
K(q 0 , t0 ; q, t) = [dq]ei t Ldt
Z m n/2 2 2 2
= lim dq1 · · · dqn−1 e(im/2)[(qn −qn−i ) +(qn−1 −qn−2 ) ···+(q1 −q0 ) ] (9.11)
n→∞ 2πi
The integral over q1 can be done to obtain
Z r
(im/2)[(q1 −q)2 +(q2 −q1 )2 ] πi (im/4)[(q−q2 )2 ]
dq1 e = e
m
Z m n/2 r πi 2 2 +(q−q2 )2 /2]
K = lim dq2 · · · dqn−1 e(im/2)[(qn −qn−i ) ···+(q3 −q2 ) (9.12)
n→∞ 2πi m
The integral over q2 is

9.1. DEFINITIONS 211
Z r
(im/2)[(q3 −q2 )2 +(q2 −q)2 /2] 4πi (im/6)[(q−q2 )3 ]
dq2 e = e (9.13)
3m
and so on. Thus one obtain
s r
m n/2 m n/2 r πi r 4πi (n − 2)πi (n − 1)πi (im/2n)(q−q0 )2
0 0
K(q , t ; q, t) = lim ··· e
n→∞ 2πi 2πi m 3m (n − 1)m nm
r
m im (q − q 0 )2
= exp (9.14)
2πi(t − t0 ) 2 t − t0
On another side it can be computed as (with ω = E = p2 /2m)
Z
dp
K(q 0 , t0 ; q, t) = < q 0 t0 |qt >= exp[−i(pq − ωt)] exp[i(pq 0 − ωt0 )]
2π
Z 2
dp p 0 0
= exp −i (t − t) − p(q − q)
2π 2m
r
m im (q − q 0 )2
= exp (9.15)
2πi(t − t0 ) 2 t − t0
9.1.5 Example: harmonic oscillator

9.1.6 Path Integral properties
Several properties of the path integrals are
Z
ψ(x, t) = K(xt, x0 t0 )ψ(x0 t0 )dx0
Z
|x, t > = |x0 t0 >< x0 t0 |x, t > dx0 (9.16)
similarly
Z
K ∗ (xt, x0 t0 )K(xt, x00 t00 )dx = δ(x0 − x00 )
Z
< x0 t0 |x, t >< x, t|x00 t00 > dx = δ(x0 − x00 ) (9.17)
The time evolution operator is defined as K(t) = exp[−iHt], with K(0) = 1. It satisfy the SE
i∂K/∂t = HK and allow us to transform from the Schrödinger picture to the Heisenberg one:
|ψ(t) >S = K(t)|ψ(0) >S , OH (t) = eiHt OS e−iHt = K(t)† O(0)K(t) (9.18)
Several properties are

K(t1 + t2 ) = K(t1 )K(t2 ), K(t)K(t)† = 1

X
K(t) = e−iEn t |n >< n|, H|n >= En |n >, < n|l >= δnl (9.19)
n
the spectral representation. In the q-representation
0
K(q 0 t0 , qt) =< q 0 |K(t0 − t)|q >=< q 0 |e−iH(t −t) |q >=< q 0 t0 |qt > (9.20)
On another side
K(t0 − t) = K(t0 − tn−1 + tn−1 + · · · + t2 − t1 + t1 − t) = K(t0 − tn−1 )K(tn−1 − tn−2 ) · · · K(t1 − t)

Z
K(q t , qt) = < q |K(t − t)|q >= dqn−1 · dq1 < q 0 |K(t0 − tn−1 )|qn−1 >< qn−1 |K(tn−1 − tn−2 )
0 0 0 0
|qn−2 >< qn−2 | · · · |q1 >< q1 |K(t1 − t)|q > (9.21)
Each term can be worked out
2
< ql |K(tl − tl−1 )|ql−1 > = < ql |e−iH |ql−1 >= e−iVl−1 < ql |e−ip /2m |ql−1 >
Z Z
dp 2 dp −ip2 /2m
= e−iVl−1 < ql |e−ip̂ /2m |p >< p|ql−1 >= e−iVl−1 e < ql |p >< p|ql−1 >
2π 2π
Z r r
−iVl−1 dp −ip2 /2m ip(ql −ql−1 ) −iVl−1 m −im·ql−1
2 /2 m iLl−1
= e e e =e e = e (9.22
2π 2πi 2πi
and one obtains the usual representation for the Path Integral
Z " Z #
t0
0 0
K(q t , qt) = lim dqn−1 · dq1 exp i Ldt (9.23)
n→∞ t
9.1.7 Spectra
Giving that
X X 0
K(t) = e−iEn t |n >< n|, K(q 0 t0 , qt) = e−iEn (t −t) ψn∗ (q 0 )ψn (q) (9.24)
n n
thus on obtains the spectra and the eigenfunctions as the limits
X
lim K(q 0 , −iT ; q0) = e−En T ψn∗ (q 0 )ψn (q) = e−E0 T ψ0∗ (q 0 )ψ0 (q)
T →∞
n
0 −(E1 −E0 )T
lim K(q , −iT ; q0)e E0 T
= e ψ1∗ (q 0 )ψ1 (q) + ψ0∗ (q 0 )ψ0 (q)
T →∞
lim K(q 0 , −iT ; q0)eE0 T = e−(E2 −E0 )T ψ2∗ (q 0 )ψ2 (q) + e−(E1 −E0 )T ψ1∗ (q 0 )ψ1 (q) + ψ0∗ (q 0 )ψ0 (q)(9.25)
T →∞
9.2. SEMICLASSICAL APPROXIMATION 213
9.1.8 Expectation values

Z " Z #
t0
< q 0 t0 |O(t1 )|qt > = [dq]O(t1 ) exp i Ldt
t
Z " Z #
t0
0 0
< q t |T [O(t1 )O(t2 )] |qt > = [dq]O(t1 )O(t2 ) exp i Ldt (9.26)
t
and in general
Z " Z #
t0
0 0
< q t |T [O(t1 ) · · · O(tn )] |qt > = [dq]O(t1 ) · · · O(tn ) exp i Ldt
t
Z
< 0|T [O(t1 ) · · · O(tn )] |0 > = dqdq 0 < 0|qt >< qt|T [O(t1 ) · · · O(tn )] |q 0 t0 >< q 0 t0 |0 >
Z
= dqdq 0 ψ0 (qt)ψ0∗ (q 0 t0 ) < qt|T [O(t1 ) · · · O(tn )] |q 0 t0 > (9.27)
A generating function can be defined as
Z " Z #
t0
Z(J) = [dq] exp i [L + Jq] dt
t
Z
= dqdq 0 ψ0∗ (q 0 t0 )ψ0 (qt)Z[J]
1 δ n Z[J]
< q 0 t0 |T [O(t1 ) · · · O(tn )] |qt > = (9.28)
in δJ(t1 ) · · · δJ(tn )
9.2 Semiclassical Approximation

In general all the paths contribute to the integral however in many cases the largest contribution is
given by the classical trajectory. This is the principle behind the WKB or semiclassical approximation.
Let’s expand the action around the classical trajectory, qc :
Z Z
S[q] = L(q, q̇)dt = L(qc + y, q̇c + ẏ)dt
Z
δL δL 1 δ2L 2 1 δ2L 2 δ2L
= dt L(qc , q̇c ) + y+ ẏ + y + ẏ + y ẏ + · · ·
δq δ q̇ 2 δq 2 2 δ q̇ 2 δqδ q̇
Z 2
1 δ L 2 1 δ2L 2 δ2L
= S[qc ] + dt y + ẏ + y ẏ + · · · (9.29)
2 δq 2 2 δ q̇ 2 δqδ q̇
where the linear part contribution vanish given that at the classical trajectory we have a minima
and the Euler Lagrangian equations are obtained
d δL δL
= (9.30)
dt δ q̇ δq
9.2.1 Example: the harmonic oscillator

In this case
m 2
L = q̇ − ω 2 q 2 (9.31)
2
9.3 Quantum Fields: Scalars, Fermions.
9.4 Perturbation Theory. Feynmann diagrams.
9.5 Loop expansion. Effective potential

Chapter 10
QM References
215
216 CHAPTER 10. QM REFERENCES
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Appendix A
Constants and Formulae
A.1 Constants, units
~ = 10−34 J · s = 6.6 · 10−22 MeV · s, ~c = 197.3 MeV · fm = 1973 eV · Å, (~c)2 = 0.0389 (GeV · fm)2
m J eV
α−1 = 137.035, λvisible = [3800 − 7600] Å, c = 3 · 108 , kB = 1.38 · 10−23 o = 8.62 · 10−5 o
s K K
−31 −27
me = 0.5 MeV = 9.1 · 10 Kg, mp = mn = uma = 938 MeV = 1.7 · 10 Kg,
mµ = 105.7 MeV, mπ = 139.6 MeV
µB = e/2me = 5.8 · 10−5 eV /T = 9.3 · 10−24 J/T, µN = e~/2mp ' 3.15 · 10−8 eV/Telsa
G = 6.7 · 10−11 N · m2 /K2 , M = 1.99 · 1030 K, M⊕ = 5.98 · 1024 K, M◦ = 7.34 · 1022 K
R⊕ = 1.5 · 1011 m, R⊕◦ = 3.84 · 108 m, R⊕ = 6380Km, T◦ = 27.322 days
1eV = 1.6 · 10−19 Jul. = 2.4 · 1014 hz, 1 cm−1 = 1.24 · 10−4 eV = 3 · 1010 hz
natural units : ~ = c = e = 1, α = 1/4π0 = µ0 /4π, [F] = [E] = [B] = eV2 (A.1)
kind ν [hz] λ [m] E [eV] kind ν [1014 hz] λ [10−7 m]

radio 5· 105 − 1.6 · 108 0.2 − 700 (0.01 − 7) · 10−6 red 3.84-4.82 6.22-7.8
MW 109 − 1012 1 − 10−3 10−5 − 0.001 orange 4.82-5.03 5.97-6.22
IR 3 · 1011 − 4 · 1014 10−3 − 10−6 0.001 − 1.65 yellow 5.03-5.2 5.77-5.97
visible (4 − 7.5)1014 (0.4 − 0.8) · 10−6 1.65 − 3.1 green 5.2-6.1 4.92-5.77
UV (0.8 − 30) · 1015 4 · 10−7 − 10−8 3.1-124 blue 6.1-6.59 4.55-4.92
r. X 3 · 1016 − 3 · 1019 10−8 − 10−11 124 − 106 violet 6.59-7.69 3.9-4.55
r. γ > 1020 < 10−12 > 106
227
228 APPENDIX A. CONSTANTS AND FORMULAE
A.2 Useful formulae 1-D
m 3 ∂ρ i 1
< v2 > = kB T, = −∇ · J, ρ = |ψ|2 , J = [ψ∇ψ ∗ − ψ ∗ ∇ψ] = Im[ψ ∗ ∇ψ], [xi , pj ] = iδij
2 2 ∂t 2m m
2π~c k
p = ~k = −i~∇, E = p2 /2m = ~ω, k = 2π/λ, λ = √ JI = (|A|2 − |B|2 ) , T = ma2
2
E −m c 2 4 m
r
2 nπx 2
n π 2
ψn = sin En =
a a 2ma2
2 √
ψn = Nn e−ξ /2 Hn (ξ), En = (n + 1/2)ω, |Nn |2 = α/2n π n!, ξ = αx, α2 = mω
Z ∞
2 √
2xHn (x) = Hn+1 (x) + 2nHn−1 (x), Hn0 (x) = 2nHn−1 (x), dx e−x Hn (x)Hm (x) = 2n n! πδnm(A.2)
−∞
1 h√ √ i iα h√ √ i
xn,l = √ l + 1δn,l+1 + lδn,l−1 , pn,l = √ l + 1δn,l+1 − lδn,l−1
2α 2
1 hp p i
x2n,l = (l + 1)(l + 2)δ n,l+2 + (2l + 1)δn,l + l(l − 1)δ n,l−2
2α2
α 2 hp p i
p2n,l = − (l + 1)(l + 2)δn,l+2 − (2l + 1)δn,l + l(l − 1)δn,l−2 , x3nn = p3nn = 0
2
3 1 3α4 1
x4nn = n(n + 1) + , p 4
nn = n(n + 1) + (A.3)
2α4 2 2 2
A.3 Useful formulae 3-D
ET = ECM + Erel. , 2 < K >=< r · ∇V (r) >

r n πx n πy n πz
8 1 2 3 1 n 1 π 2 n 2 π 2 n 3 π 2
ψ = sin sin sin , En1 n2 n3 = + +
V a b c 2m a b c
r
α1 α2 α3
ψ(x) = exp[−(ξ12 + ξ22 + ξ32 )/2]Hn (ξ1 )Hn (ξ2 )Hn (ξ3 )
2 n 1 +n 2 +n 3 n !n !n !π 3/2
1 2 3
kf2 eB
E = (n1 + 1/2)ω1 + (n2 + 1/2)ω2 + (n3 + 1/2)ω3 , En = (n + 1/2)Ω + , Ω= (A.4)
r 2m m
2
ψklm = kjl (kr)Ylm (θ, φ), E = k 2 /2µ
π
1 a3 2 x2nl
Rnl = Anl jl (xnl r/a)Ylm (θ, φ), = [jl+1 (xnl )] , Enl = , (jl (xnl ) = 0; xns = nπ, xnp = 4.5, 7.7)
|Anl |2 2 2µa2
Enl = V0 (ξnl 2
/c2 − 1) (A.5)

−ρ2 /2 l 2l + 3 2
ψnlm = Nnl e ρ F −n, , ρ Ylm , En,l,m = (2n + l + 3/2)ω
2
Γ(n + l + 3/2)
|Nnl |2 = 2(µω)3/2 (A.6)
Γ(n + 1)Γ2 (l + 3/2)
A.4. FORMALISM FORMULAE 229
2 (n − l − 1)! 4
ψnlm = Nnl e−ρ/2 ρl L2l+1
n−l−1 (ρ)Ylm , |Nnl | = , En = −(µ/2) · (Zα/n)2
(n + l)! n4 a3

1 aµ −8 1 1 3 Zα
a = = , aB = 0.53 · 10 cm, |ψnlm (r = 0)| =
Coul. 2
, vrms =
Zαµ Z π na n

1 1 1 1 1 1 1 l(l + 1)
= , = 3 , = 3 , < r >= 1 + 1− n2 aµ
r n2 a r2 n (l + 1/2)a2 r3 n l(l + 1/2)(l + 1)a3 2 n2
3/2
Z −Zr/a0 Z 3/2 Zr −Zr/2a0 1 Z 3/2 Zr −Zr/2a0
R1s = 2 e , R2s = 2 1− e , R2p = √ e (A.7)
a0 2a0 2a0 3 2a0 a0
A.4 Formalism formulae
X X
|n >< n| = 1, ψn (x)∗ ψn (y) = δ(x − y)
n n

α ip † α ip
a= √ x+ 2 , a = √ x − 2 , [a, a† ] = 1, α2 = mω
2 α 2 α
†
√ √
a |n >= n + 1|n + 1 >, a|n >= n|n − 1 >
1
∆f ∆g ≥ |h|, [f, g] = ih
2
d<f > ∂ < f > df ∂f
= i h[H, f ]i + , = i[H, f ] +
dt ∂t dt ∂t
d
= hF = −∇Ui , 2 < K >=< r · [∇V ] >
dt
|ψ(t) >H = exp[itH]|ψ(t) >S , fH = exp[itH]fS exp[−itH]
|ψ(t) >I = exp[itH0 ]|ψ(t) >S , fI = exp[itH0 ]fS exp[−itH0 ] (A.8)
A.5 Angular Momenta
[Ji , Jj ] = iijk Jk , [J+ , J− ] = 2Jz , [Jz , J± ] = ±J± , J 2 = J± J∓ + Jz2 ∓ Jz = (J− J+ + J+ J− )/2 + Jz2
p p
J± |jm >= (j ∓ m)(j ± m + 1)|l, m ± 1 >== j(j + 1) − m(m ± 1)|l, m ± 1 >, J± = Jx ± iJy
r r
2l + 1 (l − m)! 1/2 1 3 3 ±iφ
Ylm = (−1) e Pl (cos θ), Y00 = √ ; Y10 =
m imφ m
cos θ, Y1±1 = ∓ e sin θ
4π (l + m)! 4π 4π 8π
Z
∗ l(l + 1)
dΩ = dφdx, dΩYlm Yl0 m0 = δll0 δmm0 , El = , E = −gµB Bm
2I
  " #
0 1 0 2
2 1 1 L2 Ly L 2
J+ =  0 0 1  , Iesfera = mr2 , Idisco,eje = 2Idisco,diametro = mr2 , H = x
+ + z
5 2 2 Ix Iy Iz
0 0 0

0 1 0 −i 1 0
σ1 = , σ2 = , σ3 = (A.9)
1 0 i 0 0 −1
A.6 Perturbations theory
(1)
0
Hln X 0 |2
|Hnm X
0 0
En(1) = Hnn , Cnl = (0) (0)
[1 − δnl ], En(2) = (0) (0)
, Hlm − δlm En(1) Cnm
(0)
=0
En − El m6=n En − Em m
(1) 1 − δnl X X
0 0 0
Cnl = (0) (0)
Hlm (0)
Cnm , iċn (t) = eiωnm t Hnm (t)cm , Hnm (t) =< n|H 0 (t)|m >
En − El m∈n m
Z Z
b p C p
pdx = (n + 1/2)π, p = 2m(E − V ), ψWKB (x) ' √ exp ±i p dx , p = 2m(E − V(A.10)
)
a p
A.7 Matter
2 p
Zα 3 n
∆E = −En − , K = p2 + m2 − m
n 4 J + 1/2

2 2 −1/2
2 1/2
EnJ = m 1 + (Zα) / n − J − 1/2 + (J + 1/2) − (Zα)
2
−m

gI µ3 4 Z 3 F (F + 1) − I(I + 1) − J(J + 1) J(J + 1) + S(S + 1) − l(l + 1)
∆E = α , g =1+
2 mM n J(J + 1)(2l + 1) 2J(J + 1)
0
∆E = µB gmJ B, ∆E = µB (ml + 2ms )B, H = eEz
(
me α(Zα)4 k(n, 0), l=0
∆E = · , 12.7 < k(n, 0) < 13.3, k(n, l > 0) < 0.05
4n 3
k(n, l) ± 1/π(j + 1/2)(l + 1/2), j = l ± 1/2

mα 4

11 1 + jl /2
−(3l + 4)/(l + 1)(2l + 3) ifj = l + 1

∆Enjl = − , jl = 1/l(l + 1) ifj = l (A.11)
2n3 32n 2l + 1 

(3l − 1)/l(2l − 1) ifj = l − 1
A.8 Radiation
r
dΓ α 3 4α 3 n
= ωba |~ · ~rba | , Γ =
2
ωba |rba | , xn,n−1 = xn−1,n =
2
dΩ 2π 3 2mω
a a a
< 2p , m = 1|r|1s >= − √ (1, −i, 0) , < 2p, m = −1|r|1s >= √ (1, i, 0) < 2p, m = 0|r|1s >= √ (0, 0, 1)
6 6 3
5
4! 2 a0
a = √ , ˆ1 = (−cθ cφ , −cθ sφ , sθ ), ˆ2 = (−sφ , cφ , 0) (A.12)
6 5 Z
A.9 Scattering
X 2l + 1 Z ∞
4π X 2
σ = (2l + 1) sin (δl ) , f (θ) =
2
e2iδl
− 1 Pl (cos(θ)), δl ' 2mk 2l+1
[(2l + 1)!!] drr2(l+1) V (r)
k2 2ik 0
l l
2 Z Z
dσ 2mZα 2 m 1
= F (q 2 ) , f (q) = d3 x eiq·x V (x), F (q) = d3 x eiq·x ρ(x), q = kfin. − kin. (A.13)
dΩ q 2 2π Qtotal
A.10. INTEGRALS 231
A.10 Integrals
Z Z Z ∞
x sin(2ax) x2 x sin(2ax) cos(2ax) n!
sin (ax)dx = −
2
, x sin (ax)dx =
2
− − , drrn e−ar = n+1
2 4a 4 4a 8a2
0 a
Z Z
x sin(2ax) x 2 x sin(2ax) cos(2ax)
cos2 (ax)dx = + , x cos2 (ax)dx = + +
2 4a 4 4a 8a2
Z Z
sin (ax)
2
x 3 x 2 1 x cos(2ax)
sin(ax) cos(ax)dx = , x2 sin2 (ax)dx = − − 3 sin(2ax) −
2a 6 4a 8a 4a2
Z ∞ r Z ∞ r
2 1 π 2 1 π
dx e−ax = , dx x2 e−ax = (A.14)
0 2 a 0 4a a
Appendix B
Math
B.1 Basic Math

n
X n
X
n n!
(a + b) =
n
a b =
n−k k
an−k bk (B.1)
k k!(n − k)!
k=0 k=0
B.1.1 Trigonometry
Trigonometric identities are

1 1+x i 1 + ix
tanh−1 (x) = ln , tan−1 (x) = − ln (B.2)
2 1−x 2 1 − ix
and tanh(ix) = i tan(x), tanh−1 (ix) = i tan−1 (x), tan−1 (1/x) = − tan−1 (x) ± π/2 and tan(x +
nπ) = tan(x)
B.1.2 Quadratic (Conic) Plots

Ax2 + Bxy + Cy 2 + Dx + Ey + F = 0 (B.3)
with I = B 2 − 4ACand tan(2θ) = A−C .
If I = 0 it is a parabola, if I < 0 is an ellipse and if I > 0
B
is a hyperbola. [AB, C] = A {C, B} − {C, A} B Roman p. 65.
B.1.3 Vectorial Calculus
a · (b ∧ c) = (a ∧ b) · c
a ∧ (b ∧ c) = b(a · c) − c(a · b)
∇(A · B) = (A · ∇)B + (B · ∇)A + B ∧ (∇ ∧ A) + A ∧ (∇ ∧ B)
∇ · (f A) = (∇f ) · A + f (∇ · A)
∇ · (A ∧ B) = B · (∇ ∧ A) − A · (∇ ∧ B)
∇ ∧ (f A) = (∇f ) ∧ A + f (∇ ∧ A)
∇ ∧ (A ∧ B) = (B · ∇)A − (A · ∇)B + (∇ · B)A − (∇ · A)B
∇ ∧ (∇ ∧ B) = ∇(∇ · A) − ∇2 A (B.4)
233
234 APPENDIX B. MATH
B.1.4 Curvilinear coordinates
X
dr = hi dqi ui , d2 V = Πi hi dqi
i
X 1 ∂
∇ = ui
hi ∂qi
i

1 ∂h2 h3 A1 ∂h1 h3 A2 ∂h1 h2 A3
∇·A = + +
h1 h2 h3 ∂q1 ∂q2 ∂q3

h1 u1 h2 u2 h3 u3
1
∂/∂q1 ∂/∂q2 ∂/∂q3

∇∧A =
h1 h2 h3
h1 A1 h2 A2 h3 A3

1 ∂ h2 h3 ∂ ∂ h1 h3 ∂ ∂ h1 h2 ∂
∇ =
2
+ + (B.5)
h1 h2 h3 ∂q1 h1 ∂q1 ∂q2 h2 ∂q2 ∂q3 h3 ∂q3
(q1 , q2 , q3 ) h1 h2 h3 u1 u2 u3
(x, y, z) 1 1 1 i j k
(r, θ, φ) 1 r r sin θ ur uθ uφ
(ρ, φ, z) 1 ρ 1 uρ uθ uz
Table: Curvilinear coordinates.
1 ∂ 2∂ 1 ∂ ∂ 1 ∂2 1 ∂ ∂ 1
∇2 = r + sin θ + = 2 r2 − L2
r2 ∂r ∂r r2 sin θ ∂θ ∂θ r2 sin θ ∂φ2
2 r ∂r ∂r r2
∂2 1 ∂ 1 ∂2 ∂2
= + + + (B.6)
∂ρ2 ρ ∂ρ ρ2 ∂φ2 ∂z 2
B.1.5 Dirac’s delta
X δ(x − xi )
δ (f (x)) = , δ(x) = θ0 (x)
|f 0 (xi )|
i
Z
f (x)δ 0 (x − a)dx = −f 0 (a), xδ 0 (x) = −δ(x)
1 n
δ (n) (x − x0 ) = Π δ(ξi − ξi0 )
|J| i=1
δ(r − r0 ) (2) δ(r − r0 ) δ(θ − θ0 )δ(φ − φ0 ) δ(r − r0 )
δ (3) (x − x0 ) = δ (Ω − Ω 0
) = = δ(t − t0 )δ(φ − φ0 )
r2 r2 sin θ r2
δ(ρ − ρ0 )
= δ(z − z 0 )δ(φ − φ0 ) (B.7)
ρ
where |J| = Πni=1 hi (Morse Feshbach). Several representations are (Liboff [1] and Byron and Fuller
in [QM formalism])
B.1. BASIC MATH 235
Z Z
1 ∞
1 ∞
δ(x) = dk eikx = dk cos(kx)
2π −∞ π 0
∞
" ∞
#
1 X 1 X
δ(x) = einx = 1+2 cos(nx)
2π −∞
2π
n=1
1 1 sin(ax) 1 1 − cos(ax)
δ(x) = lim √ exp[−x2 /a2 ] = lim = lim
a→0 a π π a→∞ x π a→∞ ax2
2 sin2 (ax/2) 1 a 1 1
δ(x) = lim = lim = lim Im
π a→∞ ax 2 a→0 π x + a
2 2 π a→0 x − ia
(2n + 1)!
δ(x) = lim 2n+1 (1 − x2 )n θ(1 − x) (B.8)
n→∞ 2 (n!)2
B.1.6 Complex Analysis

The Cauchy’s Theorem is given as [5]
I X
f (z)dz = 2πi n(Γ, zi )resf (zi )
Γ res.
1 dm−1
res.f (zi ) = lim [(z − zi )f (z)]
(m − 1)! z→zi dz m−1
I
f (z)dz 2πi
= f (n−1) (ζ) (B.9)
C (z − ζ)n (n − 1)!
with the positive sign if the contour integral is counterclockwise, otherwise a minus sign has to be
added.
B.1.7 Analytical Integrals

Gaussian Integrals
Z Z ∞ r
∞
n −ax Γ(n + 1) n! 2n −ax2 (2n − 1)!! π
x e dx = = n+1 , x e dx =
0 an+1 a −∞ (2a)n a
Z ∞ r Z ∞ r
2 π b2 /4a 2 π d b2 /4a
n
e−ax +bx dx = e , xn e−ax +bx dx = e
−∞ a −∞ a dbn
Z ∞ r Z ∞ r
−ax2 +bx π b b2 /4a 2 −ax2 +bx π 1 b2 2
xe dx = e , x e dx = 1+ eb /4a
a 2a a 2a 2a
Z−∞∞
−∞
2 √ 2 √
e−x /4a−bx dx = πaeab 1 − Erf(b a) (B.10)
0
with Erf(x) the error function (Abramowitz 295)

 √ √ 2
Z  1
log 2ax + b + 2 a ax + bx + c , if a > 0
dx √
a h i
√ =
Y  √1 sin−1 √−2ax−b , if a < 0
−a b2 −4ac
 √
2ax+b−√b2 −4ac
 √b2 −4ac log 2ax+b+ , if b2 > 4ac
 1
Z  h b2 −4ac
i
dx
= √ 2 tan−1 √2ax+b , if b2 < 4ac
Y 
 4ac−b2 4ac−b2
 2
− 2ax+b , if b2 = 4ac
 √
b2 −4ac
Z (x + 2a ) log Y − 2x + √ a
 b
tanh−1 √2ax+b , if b2 > 4ac
 h b2 −4aci
dx log Y =
2
(x + 2a b
) log Y − 2x + 4ac−b a tan−1 √2ax+b , if b2 < 4ac

 √ √ √ √ 4ac−b2
 √2 [ a x + c] [log( a x + c) − 1] , if b2 = 4ac
a
Z Z 2
x 1 x 2x 2
xe dx =
ax
− e ,
ax
x e dx =
2 ax
− 2 + 3 eax (B.11)
a a2 a a a
with Y = ax2 + bx + c (CRC p. 390). From Landau p. 242 [5]

Z ∞
dk
P =0 (B.12)
0 k − k22
2
B.1.8 Relativity and Tensors
xµ = (t, ~x), g µν = diag.(1, −1, −1, −1), xµ = (t, −~x), s2 = gµν xµ xν = t2 − (~x)2 (B.13)

∂ ∂ ~ ∂ ∂ ~ ∂xν
∂µ ≡ = µ
,∇ , ∂ ≡ = , −∇ , ∂ µ xν = gνµ = = δµν (B.14)
∂xµ ∂t ∂xµ ∂t ∂xµ

dxµ d2 xµ ∂ ~
µ
v ≡ = γ(1, ~v ), aµ ≡ 2 , pµ = i∂ µ = i , −∇ (B.15)
dτ d τ ∂t
pµ = (E, p~) = mγ(1, ~v ) = mv µ , v µ vµ = 1

~ k µ = (ω, ~k), F µ = maµ , Aµ = (φ, A),
J µ = (ρ, J), ~ γ µ = (γ 0 , γ i ) (B.16)
 
0 −Ex −Ey −Ez
 Ex 0 −Bz By 
F µν = ∂ µ Aν − ∂ ν Aµ = 
 Ey Bz

0 −Bx 
Ez −By Bx 0
 
0 −Bx −By −Bz
1 µναβ  Bx 0 Ez −Ey 
∗
F µν = Fαβ =  
 (B.17)
2 By −Ez 0 Ex 
Bz Ey −Ex 0
B.2. SPECIAL FUNCTIONS 237
1
F µν = − µναβ ∗ Fαβ
2
~2 − B
F µν Fµν = −∗ F µν ∗ Fµν = −2(E ~ 2 ) F µν ∗ Fνρ = g µ E
~ ·B
~ (B.18)
ρ
∂A
E = −∇A0 − , B=∇∧A (B.19)
∂t
The Pauli matrices have the following properties:
σiσj = δ ij + iijk σ k , σ · a σ · b = a · b + iσ · (a ∧ b)

0 1 0 −i 1 0
σ1 = , σ2 = , σ3 = (B.20)
1 0 i 0 0 −1
[σi , σj ] = 2iijk σk , {σi , σj } = 2δij , ~σ ×~σ = 2i~σ , they are traceless and trσi σj = 2δij .
The totally antisymmetric tensor satisfy
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
µναβ µ ν α β = −g µµ g νν g αα g ββ + g µµ g νν g αβ g βα − g µµ g νβ g αν g βα + · · · = −det(g σσ )
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
µναβ µ ν α β = −g µµ g νν g αα + g µµ g να g αν − g µα g νµ g αν + g µα g νν g αµ + · · · = −det(g σσ )
0 0
0 0 0 0
0 0
µναβ µ ν αβ = −2 g µµ g νν − g µν g νµ , µναβ µ ναβ = −6g µµ , µναβ µναβ = −4! = −24 (B.21)
where in the first case σ = µ, ν, α and β (to form a 4 × 4 determinant), in the second case
σ = µ, ν and α (to form a 3 × 3 determinant), and similarly for σ 0 . The 3D version is
ijk lmk = δ il δ jm − δ im δ jl , ikl ikm = 2δ lm , ikl ikl = 3! (B.22)
B.2 Special Functions

B.2.1 Bessel functions
Bessel functions are the solutions (Jν (x): Bessel function of first kind and Nν (x) = Yν (x): Bessel
function of second kind, Weber or Neumann function) to the Bessel equation

1 ν2
Jν00 (r) + Jν0 (x) + 1 − 2 Jν (x) = 0 (B.23)
r ρ
From them one can define Hankel functions of first and second kind (or Bessel functions of third
(1,2) (1,2) p
kind) as Hν (x) ≡ Jν (x) ± iNν (x). At infinite they behave as Hν (x → ∞) = 2/πx exp[±ix].
When the argument is pure complex one can use the modified Bessel functions of first and second
class defined as
π ν+1 (1)
Iν (x) ≡ i−ν Jν (ix), Kν (x) ≡ i Hν (ix) (B.24)
2
at x = 0 Iν (sometimes called hyperbolic Bessel function) is regular while Kν is not. At infinity

the behavior is
cos(x)
Iν (x) → , Kν (x) → e−x (B.25)
x
The Wroskian is In (x)Kn (x)0 − Kn (x)In (x)0 = −1/x (see Arfken Sturm-Liuville theory, Arfken
610, Jackson 86, Mathematica 746, Gradshteyn 960). Kelvin functions are defined as

bern (z) + ibern (z) = einπ Jn ze−iπ/4 (B.26)
The generatriz function is
∞
X
ex(t−1/t)/2 = Jn (x)tn (B.27)
n=−∞
Recurrence relations and orthogonality conditios are
2n 1
Jn+1 (x) = Jn (x) − Jn−1 (x), Jn0 (x) = (Jn−1 (x) − Jn+1 (x))
x Z ∞ 2
0 1
xJn (x) = nJn (x) − xJn+1 (x), dρρJν (αρ)Jν (α0 ρ) = δ(α − α0 )
0 α
Z a 3
a
dr r2 [Jl (xnl r/a)]2 = [Jl+1 (xnl )]2 (B.28)
0 2
B.2.2 Spherical Bessel functions

p
The spherical Bessel functions (zn (x) = π/2x ·Zn+1/2 (x))[5] obey are the solutions to the Helmholtz
eq. in spherical coordinates:
r2 R00 (r) + 2rR0 (x) + [r2 − l(l + 1)]R(x) = 0 (B.29)
the first solutions are given as

sin x sin x cos x 3 1 cos x
j0 = , j1 = 2 − , j2 = 3
− sin x − 3 2
x x x x x x

cos x cos x sin x 3 1 sin x
n0 = − , n1 = − 2 − n2 = − − cos x − 3 2
x x x x3 x x

(1) i (1) 1 i (1) i 3 3i
h0 = − eix , h1 = − + 2 eix h2 = − 2 − 3 eix (B.30)
x x x x x x
(1)
where the Hankel functions are defined as hl (x) = jl (x) ± nl (x). The recurrence relations, for
spherical Bessel functions
2l + 1 1
zl+1 = zl − zl−1 , zl0 = [lzl−1 − (l + 1)zl+1 ] (B.31)
x 2l + 1
Z a
a3
[jn+1 (xnp )]2 δpq
dr r2 jn (xnp r/a)jn (xnq r/a) = Arfken 628
0 2
Z a
a3
dr rJν (ανl r/a)jν (xνk r/a) = [Jν+1 (xνp )]2 δlk Arfken 628
2
Z0 ∞
1
dρρJν (αρ)Jν (α0 ρ) = δ(α − α0 ) (B.32)
0 α
Asymptotic behavior
h i sin(x − lπ/2)
xl x2
jl → 1 − 2(2l+3)
(2l+1)!! + ··· jl →
x
h i cos(x − lπ/2)
nl → − (2l−1)!!
x l+1 1 − x2
2(1−2l) + · · · nl → − (B.33)
x
B.2.3 Hypergeometric functions

The hypergeometric equation and function (Abramowitz chap. 15, Arfken 749)
x(1 − x)y 00 + [c − (a + b + 1)x]y 0 − aby = 0, y1 = 2 F1 (a, , b , c ; x),

y2 = (1 − x)1−c 2 F1 [a + 1 − c, b + 1 − c, 2 − c, x]
a·b a(a + 1) · b(b + 1) 2 a(a + 1)(a + 2) · b(b + 1)(b + 1) 3
2 F1 (a, , b , c ; x) = 1 + x+ x + x + ···
1·c 1 · 2 · c(c + 1) 3! · c(c + 1)(c + 2)

(n + m)! (1 − x2 )m/2 1−x
Pnm (x) = F
2 1 m − n, m + n + 1, m + 1 ; (B.34)
(n − m)! 2m m! 2
B.2.4 Confluent Hypergeometric functions

Confluent Hypergeometric, or Kummer’s functions (Arfken p. 753, Abramowitz chap. 13, p. 503,
Gradshteyn 1084 [5]), M (a, c, x) = F (a, c, x) = Φ(a, c, x)
xy 00 (x) + (c − x)y 0 (x) − ay(x) = 0

ax a(a + 1) x2
y(x) = 1 F1 (a, c; x) = M (a, c; x) = 1 + + + ··· , c 6= 0, −1, −2, · · ·
c 1! c(c + 1) 2!
y(x) = x1−c M (a + 1 − c, 2 − c; x), c 6= 2, 3, 4 · · · Second solution

π M (a, c; x) x M (a + 1 − c, 2 − c; x)
1−c
U (a, c; x) = − (B.35)
sin(πc) (a − c)!(c − 1)! (a − 1)!(1 − c)!
Its asymptotic behavior is for x → ∞


Γ(c) ex (1 − a)(c − a) (1 − a)(2 − a)(c − a)(c − a + 1)
M (a, c; x) → 1+ + + ···
Γ(a) xc−a 1!x 2!x2

1 a(1 + a − c) a(a + 1)(1 + a − c)(2 + a − c)
U (a, c; x) → 1+ + + ··· (B.36)
x a 1!x 2!x2
Their derivatives are
dn a(a + 1) · · · (a + n)
F (a, c, x) = F (a + n, c + n; x)
dxn c(c + 1) · · · (c + n)
dn
U (a, c, x) = (−1)n a(a + 1) · · · (a + n)U (a + n, c + n; x) (B.37)
dxn
Whittaker function

00 1 k 1/4 − µ2
Mkµ (x) − + + Mkµ (x) = 0
4 x x2
Mkµ (x) = e−x/2 xµ+1/2 M (µ − k + 1/2, 2µ + 1; x)
Wkµ (x) = e−x/2 xµ+1/2 U (µ − k + 1/2, 2µ + 1; x) (B.38)
µ=0
several particular cases and relations with other functions are (Hm = Hm ) [5]
µ (2n)! µ (2n + 1)!

H2n (η) = (−1)n M (−n; µ + 1/2, η 2 ), H2n+1 (η) = (−1)n ηM (−n; µ + 3/2, η 2 )
n! n!(µ + 1/2)
Ln (x) = M (−n, 1; x)
m d Γ(n + m + 1)
m
n (x) = (−1)
Lm Ln+m (x) = M (−n, m + 1; x)
dxm Γ(n + 1)Γ(m + 1)
√
erf(x) = 2x/ π M (1/2, 3/2, −x2 ), C(z) + iS(z) = zM (1/2, 3/2, ıπz 2 /2) (B.39)
µ
where Hm are the associate or generalized Hermite polynomials.
B.2.5 Airy Function

It can be defined by the differential equation

1
Φ00 − xΦ = 0, t2 Z1/3
00 0
+ tZ1/3 + t2 − Z1/3 = 0 (B.40)
9
where the changes of variables t = 2x3/2 /3 and Φ = t1/3 Z1/3 (t). Other properties are
Z ∞
1
Φ(z) = √ dt cos(t3 /3 + zt)
π 0
(
1p I (2z 3/2 /3) − I1/3 (2z 3/2 /3) for z > 0
Φ(z) = π|z| −1/3
3 J−1/3 (2|z| /3) + J1/3 (2|z| /3) for z < 0
3/2 3/2
(
1 exp[−2z 3/2 /3)] for z → ∞
Φ(z) →
2|z|1/4 2 sin[2|z|3/2 /3 + π/4] for z → −∞
Z ∞
ψ(ξ)ψ(ξ 0 )dx = δ(E 0 − E) (B.41)
0
Its roots, Φ(−xn ) = 0 can be approximated by the formula xn = [3(n − 1/4)π/2]2/3 [17]. The roots
of its first derivative, Φ0 (−yn ) = 0 can be approximated by the formula yn = [3(n + 1/2)π/4]2/3 as it
is shown in the following table
xexact
n xapprox.
n ynexact ynapprox.
2.3381074 2.32 1.018793 1.115
4.087949 4.082 3.248198 3.261
5.5205598 5.517 4.820099 4.826
6.7867081 7.784 6.163307 6.167
7.94413365 7.942 7.372177 7.375
9.0226508 9.021 8.488487 8.49
10.040174 10.039 9.535449 9.537
Table: Roots of the Airy function and its first derivative [17].
B.2.6 Polylogarithmic functions

The Polylogarithmic functions (or Spence functions) are defined as [5]
Z Z Z
0
log(1 − t) 1
log(1 − zt) − log(1−z)
tdt
Li2 (z) ≡ dt =− dt =
z t 0 t 0 et−1
∞
X
Lin (z) = z k /k n
k=1
∞
X [− log(1 − z)]n+1
Li2 (z) = Bn (B.42)
(n + 1)!
n=0
where B0 = 1, B1 = −1/2, B2 = 1/6, B4 = −1/30, B6 = 1/42, B8 = −1/30, B10 = 5/66,

B12 = −691/2730, B14 = 7/6, B16 = −3617/510, B18 = 43867/798, · · · are the Bernoulli numbers,
that allow to compute the functions with an accuracy of 13 decimal places por n = 14.
Special values are Li2 (1) = π 2 /6, Li2 (−1) = −π 2 /12, Li2 (1/2) = π 2 /12−(1/2) log2 (1/2), Li2 (0) = 0
and useful relations are
1
Li2 (z) + Li2 (−z) = Li2 (z 2 )
2
π2 1
Li2 (z) + Li2 (1/z) = − − log2 (−z)
6 2
π2
Li2 (z) + Li2 (1 − z) = − log(z) log(1 − z)
6
z 1
Li2 (z) + Li2 − = − log2 (1 − z)
1−z 2

x y x y
Li2 · = Li2 + Li2 − Li2 (x) − Li2 (y) − log(1 − x) log(1 − y)
1−x 1−y 1−y 1−x

1−y 1−x 1−x 1−y
Li2 [x] + Li2 [y] = Li2 [xy] + Li2 x + Li2 y − log log (B.43)
1 − xy 1 − xy 1 − xy 1 − xy
The last one is the Abel’s equation and the one before it is the Landen’s functional equation.
B.2.7 Error, Fresnel and related functions

They are defined as (Abramowitz 295):
Z x
2 2
Erf(x) = Φ(x) = √ e−t dt, Erfc(x) = 1 − Erf(x)
π 0
p Z x p
C(x) = C1 ( π/2 x) = cos( π/2 t2 ) dt,
p Z 0x p
S(x) = S1 ( π/2 x) = sin( π/2 t2 ) dt, (B.44)
0
Several important properties are f(−x) = −f(x) for f=Erf, C and S. Special values are Erf(∞) =
2C(∞) = 2S(∞) = 1. The asymptotic behavior is
2 n−1
e−x X (−1)k Γ(k + 1/2) e−x
2
Erf(x) = 1 − + Rn (B.45)
π x2k+1 π
k=0
with |Rn | < Γ(n + 1/2)/|x|2n+1 cos(φ/2)and φ < π is the phase of x.
B.3 Polynomials
B.3.1 Legendre Polynomials and functions
Generation formula for Legendre Polynomials and its Rodrigues Formula (Abramowitz chap. 8, Arfken
chap. 12)
∞
X
1 1 dl 2
= tn Pn (x), for|t| < 1 Pl (x) = (x − 1)l (B.46)
(1 − 2xt + t2 )1/2 2l l! dxl
0
B.3. POLYNOMIALS 243
with P0 (x) = 1, P1 (x) = x, P2 (x) = (3x2 − 1)/2, etc., , Pl (±1) = (±1)l . Parity Pl (−x) =
(−1)l Pl (x). Orthogonality condition and recurrence relations are
Z 1
2
Pn (x)Pm (x)dx = δnm
−1 2n + 1
(2n + 1)xPn (x) = (n + 1)Pn+1 (x) + nPn−1 (x)
(1 − x2 )Pn0 (x) = nPn−1 (x) − nxPn (x)
0 0 0
(2l + 1)Pl = Pl+1 − Pl−1 , (l + 1)Pl = Pl+1 − xPl0 (B.47)
The Legendre series is
∞
X Z
2m + 1 1
f (x) = an Pn (x), with am = f (x)Pn (x)dx (B.48)
n
2 −1
Special formulas are
∞
X ∞
2n+1 (n!)2 1 1 X r< n
δ(1 − x) = , = Pn (x)
(2n + 1)! |r1 − r2 | r> r>
n=0 n=0
X∞ Z 1
e ikrx
= i (2n + 1)jn (kr)Pn (x),
n
xm Pn (x)dx = 0 for m < n (B.49)
n=0 −1
Legendre Functions of second kind

The can de defined as [5] 7.224, Atlas of functions p. 283
Z 1
Pn (x)
dx ≡ 2Qn (z)
−1 z−x
Z 1
xm
Pn (x)dx ≡ 2z m Qm (z), form ≤ n
−1 z−x
Z 1
xn+1 2n+2 (n!)2
Pn (x)dx ≡ 2z n+1 Qn (z) − (B.50)
−1 z−x (2n + 1)!
They satisfy the same recurrence relations of the Legendre polynomials in eq. (B.47), and can be
obtained by using the relation

1 1+x 2n − 1 2n − 5
Qn (x) = Pn (x) · log − Pn−1 (x) − Pn−3 (x) − · · ·
2 1−x 1·n 3 · (n − 1)

1 1+x x 1+x
Q0 (x) = log Q1 (x) = log −1
2 1−x 2 1−x

3x2 − 1 1+x 3x 5x3 − 3x 1+x 5x2 2
Q2 (x) = log − Q3 (x) = log − + (B.51)
4 1−x 2 4 1−x 2 3
m
Special values are Pl (1) = 1, P2m+1 (0) = 0, P2m (0) = (−1)
42m
(a) 2mm
Associated Legendre Polynomials and functions

One way to define them is as solutions of the Associate Legendre equation, with singularities at
z = ±1, ∞ (Abramowitz chap. 8)

d2 d µ2
(1 − z ) 2 y − 2z y + ν(ν + 1) −
2
y=0 (B.52)
dz dz 1 − z2
The general solution can be written as y = APνµ (z) + BQµν (z) with

1 z + 1 µ/2 1
Pνµ (z)= F −ν, ν + 1, 1 − µ, (1 − z)
Γ(1 − µ) z − 1 2
√ µ/2
π Γ(ν + µ + 1) (z − 1)
2 µ/2 z+1 ν+µ 1+ν+µ 3 1
Qν (z) = e
µ iµπ
F 1+ , , ν + , (B.53)
2ν+1 Γ(ν + 3/2) z ν+µ+1 z−1 2 2 2 z2
If one has the boundary condition of finiteness at z = ±1 the solution is then Plm (z), with B = 0,
ν = l = 0, 1, 2, · · · . If besides (from uniqueness of the wavefunctions) µ = m = −l, −l+1, · · · , l−1, l
dm Pl (x) (1 − x2 )m/2 dl+m (x2 − 1)l

Plm (x) = (1 − x2 )m/2 =
dxm 2l l! dxl+m
(−1) (l + m)!
m 1 dl−m (x − 1)
2 l
=
2 l! (l − m)! (1 − x )
l 2 m/2 dxl−m
X∞
(2m)!(1 − x2 )m/2
= m
Pi+m (x)ti
2m m!(1 − 2tx + t2 )m+1/2 i=0
(l − m)! m
Pl−m = (−1)m P (x), Plm (−x) = (−1)l+m Plm (x), Pl0 (x) = Pl (x), Plm>l (x) = 0
(l + m)! l
Z 1 Z 1
2δll0 (l + m)! dx 0 (l + m)!
dxPlm (x)Plm
0 (x) = , P m (x)Plm (x) =
2 l
δmm0 (B.54)
−1 2l + 1 (l − m)! −1 1 − x m(l − m)!
Merzbacher p. 387-9 and Arfken 666. Several recurrence relations are (Arfken 699)
2mx
Plm+1 = √ Plm − (l + m)(l − m + 1)Plm−1
1 − x2
(2l + 1)xPlm = (l + m)Pl−1
m
+ (l − m + 1)Pl+1
m
p
(2l + 1) 1 − x2 Plm = Pl+1
m+1 m+1
− Pl−1 = (l + m)(l + m − 1)Pl−1
m−1
− (l − m + 1)(l − m + 2)Pl+1
m−1
p m
2 1 − x2 P 0 l = Plm+1 − (l + m)(l − m + 1)Plm−1 (B.55)
Special values
2µ hπ i Γ((1 + ν + µ)/2)
Pνµ (0) = √ cos (ν + µ)
π 2 Γ(1 + (ν − µ)/2)
2 µ−1 h π i Γ((1 + ν + µ)/2)
Qµν (0) = − √ sin (ν + µ) (B.56)
π 2 Γ(1 + (ν − µ)/2)
dm Qν (x)
ν (z) = (z − 1)
Qm 2 m/2
dxm
Γ(1 + (ν + µ)/2)Γ((1 + ν + µ)/2)
W [Pνµ , Qµν ]z=0 = 22µ (B.57)
Γ(1 + (ν − µ)/2)Γ((1 + ν − µ)/2)
B.3.2 Spherical harmonics and Angular Momenta

Spherical Harmonics and Angular Momenta

∂ ±iφ ∂ ∂
Lz = −i , L± = Lx ± iLy = e ± + i cot θ
∂φ ∂θ ∂φ
1 ∂ 2 1 ∂ ∂ 1
−L2 = 2 ∂φ2 + sin θ ∂θ sin θ ∂θ = − 2 (L− L+ + L+ L− ) − Lz
2
sin θ
= −L− L+ − L2z − Lz = −L+ L− − L2z + Lz (B.58)
The commutation relations are [L+ , L− ] = 2Lz , [Lz , L± ] = ±L± and [Lz , L2 ] = [L± , L2 ] = 0
p
L2 Ylm = l(l + 1)Ylm , Lz Ylm = −mYlm , L± |l, m >= (l ∓ m)(l ± m + 1)|l, m ± 1 >
Z
∗ 2l + 1 (l − m)! 1/2
dΩ Ylm (x̂)Yl0 m0 (x̂) = δll0 δmm0 , Ylm (θ, φ) = (−1)m eimφ Plm (cos θ)
4π (l + m)!
r r r
1 3 3 ±iφ 5
Y00 = √ ; Y10 = cos θ Y1±1 = ∓ e sin θ; Y20 = 3 cos2 θ − 1
4π 4π 8π 16π
r r
15 ±iφ 15 ±2iφ 2
Y2±1 = ∓ e sin θ cos θ, Y2±2 = e sin θ, · · ·
8π 32π
1
T10 = Vz T1± = ∓ √ (Vx ± V y) (B.59)
2
p p
Particular values are Ylm (θ = 0, φ) = (2l + 1)/4π δm,0 , Yl0 = (2l + 1)/4π Pl (cos θ), Ylm =
(−1)m Yl,−m
∗ , Arfken p. 912.
l
4π X ∗
Pl (cos γ) = Ylm (Ω1 )Ylm (Ω2 )
2l + 1
m=−l
l
X X X
∗
eik·r = 4π il jl (kr)Ylm (k̂)Ylm (r̂) (Brasden), eikz = (2l + 1)il jl (kr)Pl (cos(θ))
l≥0 m=−l l≥0
~0 X l
X l
X X
eik|~x−x | (1) ∗ 1 1 1 l
r< ∗
= ik jl (kr< )hl (kr> ) Ylm (x̂)Ylm (x̂0 ), = Ylm (Ω1 )Ylm (Ω2 )
4π|~x − x~0 | 4π |r1 − r1 | 2l + 1 r>
l+1
l≥0 m=−l l≥0 m=−l
∞
X l
X
1 1
δ (3) (r − r0 ) = δ(r1 − r2 )δ(cos(θ) − cos(θ0 ))δ(φ − φ0 ) = 2 δ(r − r0 ) Ylm (θ, φ)Ylm ∗ (θ0 , φ0 ) (B.60)
r2 r
l=0 m=−l
In the case of Fourier transforms one has two useful identities (the first one is the Parseval’s one):
Z Z
d3 p
|ψ(p)| = d3 x |ψ(x)|2
2
(2π)3
Z
Rnl (k) = 4π(−i) l
dr r2 Rnl (r)jl (kr) (B.61)
where ψ(r) = Rnl (r)Ylm (r̂) and ψ(k) = Rnl (k)Ylm (k̂). Rotation matrices
(j)
Dmm0 (R) ≡ < jm| exp[−iJ · θ]|jm0 > D(j) (R) = exp[−iJ · θ]
l
X (l) (l) 4π
Ylm (Ω) ≡ Ylm (Ω0 )Dmm0 (Ω) Dmm0 (R) = Y ∗ (Ω) (B.62)
2l + 1 lm
m0 =−l
B.3.3 Gegenbauer Polynomials

Generating Function
X ∞
1
= Cnλ (t)xn (B.63)
(1 − 2tx + x2 )λ
n=0
for axample: C0λ = 1, C1λ = 2λt, C2λ = 2λ(λ + 1)t2 − λ, C3λ = (λ/3)(4λ2 + 12λ + 8)t3 − 2λ(λ + 1)t
1/2 1/2−λ
. Cn1 = Un Cn = Pn , Cnλ ∼ Pλ+n−1/2 ?. Recurrence and Orthogonality relations are
(n + 2)Cn+2
λ
(t) = 2(λ + n + 1)tCn+1
λ
− (2λ + n)Cnλ (t)
nCnλ = (2λ + n − 1)tCn−1
λ
− 2λ(1 − t2 )Cn−2
λ+1
h i
nCnλ = 2λ tCn−1
λ+1 λ+1
− Cn−2
h i
(2λ + n)Cnλ = 2λ Cnλ+1 − tCn−1
λ+1
dk ν Γ(ν + k) ν+k
Cn = 2 k Cn−k
dt k Γ(ν)
Z 1
21−2ν πΓ(2ν + n)
dt(1 − t2 )ν−1/2 Cnν (t)Cm ν
(t) = δnm (B.64)
−1 n!(n + ν)[Γ(ν)]2
They satisfy the differential equation
d2 ν d
(1 − x2 ) C − (2ν + 1)x Cnν + n(n + 2ν)Cnν = 0 (B.65)
dx2 n dx
Summation Theorem
n
Γ(2λ − 1) X 22k (n − k)![Γ(λ + k)]2
Cnλ [cos ψ cos θ + sin ψ sin θ cos φ] = (2λ + 2k − 1)
[Γ(λ)]2 Γ(2λ + n + k)
k=0
λ−1/2
sink ψ sink θCn−k
λ+k
(cos ψ) Cn−k
λ+k
(cos θ) Ck (cos φ) (B.66)
Spherical Harmonics in the 4-th dimensional space (dΩ4 = sin2 θ3 dθ3 sin θ2 dθ2 dθ1 , 0 ≤ θ2,3 ≤ π
and 0 ≤ θ1 ≤ 2π ) are
1/2
22l+1 (n + 1)(n − l)!(l!)2
|nlm > = sinl (θ3 )Cn−l
l+1
(cos θ3 )Ylm (θ2 , φ) (B.67)
π(n + l + 1)!
Special values

2ν + n − 1
Cnν (1) = (B.68)
n
B.3.4 Chebyshev Polynomials

The Chebyshev polynomials satisfy the recurrence relations (T0 = 1, T1 = x, T2 = −1 + 2x2 ) (Schaum
p. 151, Abramowicz p. 820)[5]
2xTn (x) = Tn+1 (x) + Tn−1 (x)

2Tn (x)Tm (x) = Tn+m (x) + Tn−m (x)
(1 − x2 )Tn0 = −nxTn + Tn−1
(1 − x2 )Un = xTn+1 − Tn+2
Tn (x) = cos(n cos−1 x)
sin((n + 1) cos−1 x)
Un (x) = (B.69)
sin(cos−1 x)
so (1 − t2 )Un = (Tn − Tn+2 )/2. The orthogonality conditions are

Z 1
1 0,
 if m 6= n
Tn (x)Tm (x)d x √ = π/2 if n = m 6= 0 (B.70)
−1 1 − x2 

π if m = n = 0
Their differential equation
(1 − x2 )Tn00 − xTn0 + n2 Tn = 0
(1 − x2 )Un00 − 3xUn0 + n(n + 1)Tn = 0 (B.71)
Other useful formulas are

1 X
= xn Un (t), |x|, |t| < 1
1 − 2tx + x2
m≥0
∞
X
1 − x2
= T0 (t) + 2 xn Tn (t), |x|, |t| < 1
1 − 2tx + x2
n=1
Z 1
Tn (x) d x
√ = πUn−1 (y),
−1 x − y 1 − x2
Z 1
Un (x) d x
√ = −πTn+1 (y) (B.72)
−1 x − y 1 − x2
The last two formulas are from Gradshteyn p. 1229 in [5]
B.3.5 Laguerre Polynomials

They satisfy the differential eq.
xy 00 + (1 − x)y 0 + ny = 0 (B.73)
Generating function (Use Arfken convention!)
∞
exp[−xt/(1 − t)] X tn Ln (x) ex dn n −x
= , Ln (x) = x e = F (−n, 1, x) (B.74)
1−t n! n! dxn
n=0
The Laguerre polynomials can be obtained with the recurrence relations (L0 = 1, L1 = 1 − x,
2!L2 = 2 − 4x + x2 , 3!L3 = −x3 + 9x2 − 18x + 6) (Schaum p. 151, Abramowicz p. 820)[5]
1
(n + 1)Ln+1 (x) = (2n − x + 1)Ln (x) − nLn−1 (x) → Ln+1 (x) = 2Ln − Ln−1 − [(1 + x)Ln − Ln−1 ]
Z ∞ n+1
xL0n (x) = nLn (x) − n2 Ln−1 (x), dx e−x Ln (x)Lm (x) = δnm (B.75)
0
other relations (Ln (0) = 1)
Z (
∞
p −x 0 if p < n
x e Ln (x)dx = (B.76)
0 (−1)n (n!)2 ifp = n
Associated Laguerre Polynomials
They satisfy the differential equation, etc (Arfken 755).

xy 00 + (k + 1 − x)y 0 + ny = 0
n
X
dk (−1)m (n + k)! (n + k)!
Lkn (x) = (−1)k Ln+k (x) = xm = F (−n, k + 1, x)
dxk (n − k)!(k + m)!m! n!k!
m=0
∞
X
1
exz/(1−z) = Lkn (x)z n (B.77)
(1 − z)k+1
m=0
and obey the recurrence relations (Arfken 726)
0
(n + 1)Lkn+1 (x) = (2n + k + 1 − x)Lkn (x) − (n + k)Lkn−1 (x), xLkn (x) = nLkn (x) − (n + k)Lkn−1 (x)
Z ∞ Z ∞ h i2 (n + k)!
−x k k (n + k)!
dx e x Ln (x)Lm (x) =
k
δnm , dx e−x xk+1 Lkn (x) = (2n + k + 1)
(B.78)
0 n! 0 n!
Several examples are
Lk0 (x) = 1, Lk1 (x) = k + 1 − x, Lk2 (x) = (k + 2)(k + 1)/2 − (k + 2)x + x2 /2

Lk3 (x) = −2 + x + (3 − 3x + x2 /2)(6 − x)/3 (B.79)
other relations (Lkn (0) = (n + k)!/n!k!, Lk+1

n = Lkn − Lkn−1 ?)
B.3.6 Hermite Polynomials

Generating function
∞
X Hn (ξ) 2 dn −x2
G(ξ, s) = exp[−s2 + 2sξ] = sn , Hn (x) = (−1)n ex e (B.80)
n! dxn
n=0
The Hermite polynomials can be obtained with the recurrence relations (H0 = 1, H1 = 2x,
H2 = −2 + 4x2 , H3 = −12x + 8x3 ) (Schaum p. 151, Abramowicz p. 820)[5]
Hn+1 (x) = 2xHn (x) − 2nHn−1 (x), Hn0 (x) = 2nHn−1 (x)
Z ∞
2 √
dx e−x Hn (x)Hm (x) = 2n n! πδnm (B.81)
−∞
They satisfy the differential eq.
Hn00 − 2xHn0 + 2nHn = 0 (B.82)
other relations (Arfken 755)
(2n)! (2n + 1)!

H2n (x) = (−1)n F (−n, 1/2, x2 ), H2n+1 (x) = (−1)n 2 xF (−n, 3/2, x2 )
n! n!
Hn+2 (0) = −2(n + 1)Hn (0) = (−2)n (2n − 1)!!, H2n+1 (0) = 0 (B.83)
The Associate or generalized Hermite polynomials are defined as (with Hnµ=0 = Hn )
µ (2n)! 1 µ (2n + 1)! 3 2

H2n (x) = (−1)n F (−n, µ + , x2 ), H2n+1 (x) = (−1)n xF (−n, µ + , x(B.84)
)
n! 2 n!(µ + 1/2) 2
B.4 Numerical Analysis

Finding Roots [5]
xi − xi−1
xi+1 = xi − f (xi ) (B.85)
f (xi ) − f (xi−1 )
Derivation (yi = y(xi ) and xi = x1 + h(i − 1)) :
y2 − y0 1
y 0 (x1 ) = = 2 [2y1 − 5y2 + 4y3 − y4 ]
2h h
1
y 00 (x1 ) = [−11y1 + 18y2 − 9y3 + 2y4 ] (B.86)
6h
Integrals
Z b
h3 00
I = f (ξ)
dxf (x) = h [f0 /2 + f1 + f2 + · · · + fN −1 + fN /2] − N Trapezoidal
a 12
Z b
h h5
I = dxf (x) = [f0 + 4f1 + 2f2 + · · · + 4fN −1 + fN ] − N f (4) (ξ) Simpson, N even
(B.87)
a 3 90
In the case of the trapezoidal rule for two different intervals, h = (b − a)/N (N steps) and 2h (N/2
steps) the integral is
I = Ih + kh3 N = I2h + k(2h)3 (N/2) = I2h + 4kh3 N = I2h + ∆f (B.88)
with k an unknown constant and Ih = h [f0 /2 + f1 + f2 + · · · + fN −1 + fN /2]. Solving the two

equations for the integral and the error one obtains
I = (4Ih − I2h )/3, ∆f ≡ (Ih − I2h )/3 (B.89)
Simple Montecarlo give us for the integral and for the error (in N −dimentions)
Z r
< f 2 > − < f >2
I = dV f = V < f > ±V (B.90)
V N
P PN 2
with < f >= (1/N ) N i=1 f (xi ) and < f >= (1/N )
2
i=1 f (xi ), and xi are random number
uniformly distributed inside the volume V .
B.4. NUMERICAL ANALYSIS 251
B.4.1 Gaussian Integration

Numerical Recipes Chap. 4 in [5]
Gauss-Legendre Integration
Polynomial interpolation and Gauss integration formulas are
n
X
f (x) = f (xi )Li (x)
i=1
Z 1 Xn
f (x)dx = wi f (xi ) (B.91)
−1 i=1
with Pn (xi ) = 0, the n? roots, and wi = 2/nPn0 (xi )Pn−1 (xi ) = 2(1 − x2i )/[nPn−1 (xi )]2 .
Roots and weights for Gauss-Chebyshev Integration

The Gauss-Chebyshev formula [5]
Z X n
1
f (x)dx 2π
√ ' wi f (xi ) + 2n f (2n) (ξ ∈ (−1, 1)) (B.92)
−1 1−x 2 2 (2n)!
i=1
with Tn (xi ) = 0 and wi the weights are

π π
xi = cos (i − 1/2) , i = 1, · · · , n; wi = (B.93)
n n
with TN (xN k ) = 0, xN k = cos[(k−1/2)π/N ]. The Chebyshev approximation formula is (Numerical
Recipes section 5.9 [5])
X N
1
f (x) = − c1 + ck Tk−1 (x) x ∈ [−1, 1]
2
k=1
N N
2 X 2 X 1 π 1 π
cj = f (xN k )Tj−1 (xN k ) = f cos k − cos (j − 1) k −
N N 2 N 2 N
k=1 k=1
R
ci−1 − ci+1
ci = , i > 1, c0i−1 = c0i+1 + 2(i − 1)ci , i = n, n − 1, · · · 2, c0n = c0n+1 = 0(B.94)
2(i − 1)
Once the expansion coefficients, for a given function are known those of its integral
R and derivative
can be obtained by using these recurrence relations. The integration constant is c1
The Economized power series is
∞
a0 X
f (x) = + ai Ti (x)
2
k=1
Z
2 1 dx
ai = f (x)Ti (x) √ (B.95)
π −1 1 − x2
Roots and weights for Gauss-Laguerre Integration

Table 25.9 of M. Abramowicz in ref. [5]
Z n
X Z
∞
−x [(n + 1)!]2 (2n+2) ∞
e f (x)dx ' wi f (xi ) + f (ξ ∈ (0, ∞)) g(x)dx ' wi exi g(xi )(B.96)
0 (2n + 2)! 0
i=1
with Ln (xi ) = 0, (the Zeros of Laguerre Polynomials) and wi the weight Factors.
(n!)2 (n!)2 xi
wi = = (B.97)
xi [L0n+1 (xi )]2 (n + 1)2 [Ln+1 (xi )]2
An approximate formulas for the roots are [5]:
(1 + α)(3 + 0.92α) 15 + 6.25α

x1 = , x2 = x1 +
1 + 2.4n + 1.8α 1 + 0.9α
+ 2.5n
xk+1 − xk 1 + 2.55k 1.26kα
xk+2 = xk+1 + + , k = 1, 2, · · · n − 2 (B.98)
1 + 0.3α 1.9k 1 + 3.5k
xi wi w i e xi xi wi wi exi
n=2 n=9
0.585786437627 (1)8.53553390593 1.53332603312 0.152322227732 (1)3.36126421798 0.391431124316
3.414213562373 (1)1.46446609407 4.45095733505 0.807220022742 (1)4.11213980424 0.921805028529
2.005135155619 (1)1.99287525371 1.48012790994
n=3 3.783473973331 (2)4.74605627657 2.08677080755
0.415774556783 (1)7.11093009929 1.07769285927 6.204956777877 (3)5.59962661079 2.77292138971
2.294280360279 (1)2.78517733569 2.76214296190 9.372985251688 (4)3.05249767093 3.59162606809
6.289945082937 (2)1.03892565016 5.60109462543 13.466236911092 (6)6.59212302608 4.64876600214
18.833597788992 (8)4.11076933035 6.21227541975
n=4 26.374071890927 (11)3.29087403035 9.36321823771
0.322547689619 (1)6.03154104342 0.832739123838
1.745761101158 (1)3.57418692438 2.04810243845 n = 10
4.536620296921 (2)3.88879085150 3.63114630582 0.137793470540 (1)3.08441115765 0.354009738607
9.395070912301 (4)5.39294705561 6.48714508441 0.729454549503 (1)4.01119929155 0.831902301044
1.808342901740 (1)2.18068287612 1.33028856175
n=5 3.401433697855 (2)6.20874560987 1.86306390311
0.263560319718 (1)5.21755610583 0.679094042208 5.552496140064 (3)9.50151697518 2.45025555808
1.413403059107 (1)3.98666811083 1.63848787360 8.330152746764 (−4)7.53008388588 3.12276415514
3.596425771041 (2)7.59424496817 2.76944324237 11.843785837900 (5)2.82592334960 3.93415269556
7.085810005859 (3)3.61175867992 4.31565690092 16.279257831378 (7)4.24931398496 4.99241487219
12.640800844276 (5)2.33699723858 7.21918635435 21.996585811981 (9)1.83956482398 6.57220248513
29.920697012274 (13)9.91182721961 9.78469584037
n=6
0.222846604179 (1)4.58964673950 0.573535507423 n = 12
1.188932101673 (1)4.17000830772 1.369252590710.115722117358 (1)2.64731371055 0.297209636044
2.992736326059 (1)1.13373382074 2.26068459338 0.611757484515 (1)3.77759275873 0.696462980431
(B.9
5.7751435691 (2)1.03991974531 3.350524582361.512610269776 (1)2.44082011320 1.10778139462
9.837467418383 (4)2.61017202815 4.88682680021 2.833751337744 (2)9.04492222117 1.53846423904
15.982873980602 (7)8.98547906430 7.84901594560 4.599227639418 (2)2.01023811546 1.99832760627
6.844525453115 (3)2.66397354187 2.50074576910
n=7 9.621316842457 (4)2.03231592663 3.06532151828
0.193043676560 (1)4.09318951701 0.496477597540 13.006054993306 (6)8.36505585682 3.72328911078
1.026664895339 (1)4.21831277862 1.17764306086 17.116855187462 (7)1.66849387654 4.52981402998
2.567876744951 (1)1.47126348658 1.91824978166 22.151090379397 (9)1.34239103052 5.59725846184
4.900353084526 (2)2.06335144687 2.77184863623 28.487967250984 (12)3.06160163504 7.21299546093
8.182153444563 (−3)1.07401014328 3.84124912249 37.099121044467 (16)8.14807746743 10.5438374619
12.734180291798 (5)1.58654643486 5.38067820792
19.395727862263 (8)3.17031547900 8.40543248683 n = 15
0.093307812017 (1)2.18234885940 0.239578170311
n=8 0.492691740302 (1)3.42210177923 0.560100842793
0.170279632305 (1)3.69188589342 0.437723410493 1.215595412071 (1)2.63027577942 0.887008262919
0.903701776799 (1)4.18786780814 1.03386934767 2.269949526204 (1)1.26425818106 1.22366440215
2.251086629866 (1)1.75794986637 1.66970976566 3.667622721751 (2)4.02068649210 1.57444872163
4.266700170288 (2)3.33434922612 2.37692470176 5.425336627414 (3)8.56387780361 1.94475197653
7.045905402393 (3)2.79453623523 3.20854091335 7.565916226613 (3)1.21243614721 2.34150205664
10.758516010181 (5)9.07650877336 4.26857551083 10.120228568019 (4)1.11674392344 2.7740492683
15.740678641278 (7)8.48574671627 5.81808336867 13.130282482176 (6)6.45992676202 3.25564334640
22.863131736889 (9)1.04800117487 8.90622621529 16.654407708330 (7)2.22631690710 3.80631171423
20.776478899449 (9)4.22743038498 4.45847775384
25.623894226729 (11)3.92189726704 5.27001778443
31.407519169754 (13)1.45651526407 6.35956346973
Compiled from H. E. Salzer and R. Zucker, Table of the zeros and weight factors of the first fifteen
Laguerre polynomials, Bull. Amer. Math. Soc. 55, 10041012, 1949 (with permission). NUMERICAL
ANALYSIS p. 923
B.4.2 Singular integrals

In the case of
Z Z √ Z 1
1
f (x) 1
f (x) 1 − x2 dx g(x) dx
dx = √ = √
−1 x−s −1 x−s 1−x 2
−1 x − s 1 − x2
Z Pn X n
k=1 ck Tk−1 (x) − c1 /2 √ dx
1
= =π ck Uk−2 (s) (B.100)
−1 x−s 1 − x2 k=1
√
where the ck come from the expansion of g(x) = f (x) 1 − x2 . An equivalent formula can be
obtained by using the Legendre polynomials expansion. Alternative methods are know as the Hunter’s
formula (See the e-book: Kramer and Wedmer, Computing in for cauchy principal value integral):
Knowing the weights of the numerator function, one can obtain those of the singular integral
Z 1 X
f (x) dx = wi f (xi )
−1 i
Z X
1
f (x) Q(s)/Pn (s), i = 0
dx = w̄i f (xi ), w̄i (s) = (B.101)
−1 x−s wi /(xi − s), i = 1, · · · n
i
Alternative, from M. Jensen, Computational Physics, p. 134
Z Z Z
s+
f (x) 1
f (s + t) 1
f (s + t) − f (s) 1
dx = dt = dt ' f 00 (s) · 2 + O(3 ) (B.102)
s− x−s −1 t −1 t 3
R1
where t = (x − s)/, and −1 dt/t = 0. Now the last integral is not singular!. The numerical
integral has to take an even number of steps in order to avoid the point t = 0. Additionally, it may
be practical to replace the integrand in the last expression for the derivative (or better by the Taylor
expansion), if for example an analytical expression for f is known. Similarly (Landau and Paez p.
243)
Z Z Z Z
∞
f (k) ∞
f (k) − f (k0 ) ∞
dk ∞
dk
dk = dk, = =0 (B.103)
0 k − k02
2
0 k 2 − k02 −∞ k − k0 0 k2 − k02
B.4.3 Fitting data

Fitting n data yi ± σi data, with a function f (a, x) of np parameters. It requires to minimize the
function
X f (a, xi ) − yi 2
χ 2
=
σi
∂χ2
= 0 (B.104)
∂a
To have a good fit χ ∼ n − np The error in the parameters can be as [5]
∂a ∂a
σa = δy + δx
∂y ∂x
∂ 2 χ2 ∂ 2 χ2 ∂a ∂ 2 χ2
= 0= + (B.105)
∂y∂a ∂a∂a ∂y ∂y∂a
the can be solved for ∂a/∂y

B.5 Math exercises

1.
Z b Z
b−a 1
f (x)dx = f (x(t))dt
a 2 −1
b−a b+a
x = t+ (B.106)
2 2
2.
Z Z Z Z
b fb (x) b
fb (x) − fa (x) 1
dx dyf (x, y) = dx f (x, y(t))dt
a fa (x) a 2 −1
fb (x) − fa (x) fb (x) + fa (x)
y(t) = t+ (B.107)
2 2

Understanding the Schrödinger Equation

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Understanding the Schrödinger Equation

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Contents

1 Schrödinger Equation (1-D) 11

2.3.1 Spherical Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

3 Quantum Mechanics Formalism 71

4 Angular Momentum 101

4.3.4 Magnetic dipoles in magnetic fields . . . . . . . . . . . . . . . . . . . . . . . . . 119

5 Theory of Perturbations 137

6 Topics in Atomic Physics 165

6.2.1 Zeeman effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174

8 Scattering Theory 201

8.4 Exact solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204

9 Path or Feynman Integrals 209

A Constants and Formulae 227

3.1 Quamtum jumps [Bell]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82

4.1 An infinitesimal rotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102

5.1 Figures for the Perturbation theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138

Schrödinger Equation (1-D)

4. 1752 T. Melvill observed by the first time spectral lines.

5. 1802 W. Wollaston discovers dark lines in the solar spectra.

12. 1868-70 Mendeleiev Periodic Table.

15. 1886-7 H. Hertz discovers the photoelectric effect.

17. 1897 e− is discovered by J. J. Thomson. Atomic structure (hypothesis) (Thomson): ‘plum

18. 1894-1900. Classical Physics:

20. 1901 Radioactive decays are founded to be of statistical nature.

21. 1905 Relativity and Photoelectric effect (Einstein), ~ again.

23. 1911 Atomic Structure (Rutherford). Nucleus and electrons .

25. 1914 Frank-Hertz experiment.

28. 1920 Ramsauer effect, discovered by Ramsauer and Townsend.

30. 1924 Bose-Einstein statistics and Identical particles.

31. 1925 S. Goudsmit and U. Uhlenbeck propose spin .

1.1.3 Natural Units

1.2 General properties of the Schrödinger Equation

1.2.1 Linearity, Superposition principle

1.2.2 Time Independent Schrödinger Equation

1. its solutions can be written as Ψ(t, x) = φ(t)ψ(x).

Ψ(t, x) = ψ(x) exp[−iEt] (1.3)

2. Given than in general the Time independent admits many solutions:

H(x)ψn (x) = En ψn (x) (1.4)

1.2.3 Boundary Conditions

1.2.4 Interpretation, Probability conservation

3. thus for V ∗ = V probability is conserved.

1.2.5 Expected values, Momentum space, Eigenvalues and Dirac Notation

where Nn is the number of times λn is obtained in the measurements.

6. so the predicted probability

1.2.6 Heisenberg Uncertainty principle

1.2.7 Correspondence Principle and Ehrenfest Theorem

1. a typical Action (A ' pR) is much more greater that ~.

4. Decoherent waves becomes Classical Physics

1.3 Simple Potentials

1. with ω = E = k 2 /2m = p2 /2m = (2π/λ)2 /2m,

(a) where λC = 2π/m is the Compton’s wavelength for a particle of mass m.

6. but the group velocity vg = ∂ω/∂k = v corresponds to the classical one.

7. The expectation values of the main operators are

and < x >= 0.

8. ∆x = ∞, ∆p = 0 and by he Heisenberg principle ∆x∆p ≥ 1

9. The wavefunction has to be normalized to a Dirac Delta:

12. For a plane wave one has that ψk (k 0 ) = δ(k − k 0 ).

14. A very interesting case is obtain

History and Phenomenology of de Broglie waves

in the coordinate and momentum spaces.

3. The uncertainty principle is satisfied: ∆x∆p = 1/2.

5. The complete wavefunction is given by its superposition: