EXTATIC Graduate

PHOTOIONISATION
Course
Outline
•Atomic Physics of H atom
•Multielectron Atoms: Alkalis, Helium
•Central Field Model
•Coupling Schemes
•Radiative Transitions, Oscillator Strengths, Selection Rules
•Calculations for Many Electron Atoms, Slater Integrals, Spin Orbit
Matrices etc.
•Photoabsorption
•Statistics Of Levels and Spectra: Compound Atomic States,
Unresolved Transition Arrays
•EUV Spectra of Xe and Sn
•Future directions, Sources at 6.x nm
• Conclusion

–
Internet resources used in preparing some
content
http://www.physics.ox.ac.uk/Users/Ewart/Atomic%20Physics%20Lecture%20PPT%20slides%201_8.pdf

http://www.physics.ox.ac.uk/Users/Ewart/Atomic%20Physics%20Lecture%20PPT%20slides%201_8.pdf

http://mackenzie.chem.ox.ac.uk/teaching/Atomic%20Spectroscopy.pdf

http://www.tcm.phy.cam.ac.uk/~bds10/aqp/lec12-14_compressed.pdf

http://www.tcm.phy.cam.ac.uk/~bds10/aqp/lec19_compressed.pdf

www.tcd.ie/Physics/.../lectures/js_atomic/JS_atomic_lecture1n2.ppt

www.tcd.ie/Physics/.../lectures/js_atomic/JS_atomic_lecture10-11.ppt

http://fy.chalmers.se/~f3aec/Lectures/FFY510/dipoletrans.pdf

http://ocw.usu.edu/physics/classical-mechanics/pdf_lectures/37.pdf

Lectures on Atomic Physics, Walter R. Johnson, Department of Physics, University of

Notre Dame.Notre Dame, Indiana 46556, U.S.A.
January 4, 2006

Last but not least: Wikipedia

H-Atom, summary

4
H- Wavefunctions
H-Spectrum

library.thinkquest.org
H-Like Systems
In central field for a H-like ion of charge Z V(r) α Z/r

Since energy depends only on n we have n2 degeneracy for any given En

Since Schrödinger treatment is non relativistic.

Relativistic Correction

Writing:

Since:

Off Diagonal Matrix elements therefore vanish, i.e.

and we can evaluate the perturbation simply by considering the diagonal elements.
Since
Spin Orbit Correction
Physically from the viewpoint of the electron the nucleus circulates about it givng
rise to a magnetic induction. The electron spin magnetic moment then tries to align
with the direction of B

Since the spin magnetic moment of the electron is

We get an interaction energy that depends on spin orientation

Presence of Spin Orbit interaction leads to need to switch from | n l mlms> basis to
|n l j mj> basis

The orbital angular momentum l has (if l >0) an associated magnetic moment to
which the spin angular momentum s can couple giving a total angular momentum
j, such that j= l+s i.e they add vectorially.

This gives rise to a Clebsch Gordan series

j=L+s, l+s-1, l+s-2…. |l-s|
Spin Orbit Correction
Since

For H:

Using:

Combining Relativistic, Spin Orbit and Darwin terms

Total Correction
Notation
Outline
•Background on EUVL /Current Situation
•Atomic Physics of H atom
•Multielectron Atoms: Alkalis, Helium
•Central Field Model
•Coupling Schemes
•Radiative Transitions, Oscillator Strengths, Selection Rules
•Calculations for Many Electron Atoms, Slater Integrals, Spin Orbit
Matrices etc.
•Photoabsorption
•Statistics Of Levels and Spectra: Compound Atomic States,
Unresolved Transition Arrays
•EUV Spectra of Xe and Sn
•Future directions, Sources at 6.x nm
• Conclusion

–
Hartree Theory for Multielectron Atoms

For multi-electron atoms, must consider Coulomb interactions between its Z

electrons and its nucleus of charge +Ze..
Must also consider Coulomb interactions between each electron and all other
electrons in atom.
Assume electrons are moving independently in a spherically symmetric net
potential.
The net potential is the sum of the spherically symmetric attractive Coulomb
potential due to the nucleus and repulsive Coulomb potential which represents the
average effect on the electrons in question of the Z – 1 other electrons. The
electron-electron interaction contains a large spherically symmetric component
since

Hartree theory results in a shell model of atomic structure, which includes the
concept of screening. For example, alkali atom can be modelled as having a
valence electron at a large distance from nucleus

.
Shell model
Hartree theory predicts shell model structure:
1. States are specified by four quantum numbers, n, l, ml, and ms.
2. Gross structure is determined by n and l.
3. Each (n,l) term contains 2(2l + 1) degenerate levels.
4. Pauli exclusion principle: Only two electrons with opposite spin
can occupy an atomic orbital. i.e., no two electrons have the
same 4 quantum numbers.
5. Hunds rule: Electrons fill lowest j orbital in a subshell before
pairing up with opposite spins.
Energy levels in alkali metals

• Alkali atoms: in ground state, contain a set of completely filled

subshells with a single valence electron in the next s subshell.
• Electrons in p subshells are not excited in low-energy
processes. The outer s electron is the single optically active
electron and core of filled subshells can be ignored.

hyperphysics.phy-astr.gsu.edu
Alkalis

Wave functions of electrons with

different l are found to have different
amount of penetration into the region
occupied by the 1s electrons.
This penetration exposes them more
to the influence of the nucleus and
causes them to be more tightly
bound, lowering their associated
energy states.σ
The energy of each (n, l) term of the
valence electron is
RH RH Z − ó(l )
Enl = − = =
[n − δ (l )]2 [n*]2 n2
where δ(l) is the quantum defect -
allows for penetration of the inner
shells by the valence electron.
δ(l) depends mainly on l. The wavelength of a transition is given by
1  1 1 
= R H  − 
2
λ  [n f − δ (l f )] [n i − δ (li )] 
2
Quantum Defects
Helium

Assuming each electron in helium is non-interacting, can assume each can be

treated independently with hydrogenic energy levels:
13.6Z 2
En = −
n2
Total energy of two-electron system in ground
state (n(1) = n(2) = 1) is therefore

E = E1(1) + E1 (2)
 1 1 
= −13.6Z 2 + 
 n(1) 2 n(2) 2 
1 1
= −13.6(2) 2  2 + 2 
1 1 
= −109 eV

For first excited state, n(1) = 1, n(2) = 2 => E =-68 eV.

Calculation of Ground State Energy in He

Treating the electron-electron interaction as a perturbation,

To first order, energy shift:

Summary: Ground State of He

For atomic hydrogen, ground state energy Eg = 1 Ry

He+ ion (with just a single electron) has nuclear charge Z = 2, so Eg = −22 Ry.

For He atom, if we neglect electron-electron repulsion, Eg = −2 × 22 Ry

To get a better estimate, retain form of ionic wavefunction,

but treat Z as variational parameter.
i.e. effect of electron-electron repulsion pushes wavefunction to larger radii ↔
effective reduction in Z.
The potential energy

Kinetic energy determined by trial function = Z2 Ry per electron, i.e. = 2Z2 Ry.

Contribution from electron-electron interaction,

Ground State of He

Therefore the variational state energy is:

Minimization of E(Z) w.r.t. Z gives Z = 2 − 5/16. This yields an excited state

energy of 77.5 eV which is ~ 1 eV smaller than true ground state energy.

So electron-electron interaction leads effectively to a shielding of

nuclear charge by an amount of ~(5/16)e.
Helium wavefunctions:
Spatial:
Two electron configuration. In ground state, both electrons in 1s ↔1s2 configuration.
In excited state, one or both electrons will be in higher state (e.g., 1s12s1). Configuration
can be writtenΨ=ψα (rˆ1)ψβ (rˆ2) i. e. particle #1 in a state defined by quantum numbers ,α.
State of particle #2 labelled β.
But, this does not take into account that electrons are indistinguishable, Ψ = ψ β (rˆ1 )ψα (rˆ2 )
is therefore equally valid. Because both are solutions of Schrödinger equation, linear
combination also a solution: 1
ΨS = (ψα(rˆ1)ψβ(rˆ2)+ψβ(rˆ1)ψα(rˆ2)) Symmetric
2
1
ΨA = (ψα(rˆ1)ψβ(rˆ2)−ψβ(rˆ1)ψα(rˆ2)) Asymmetric
2
Spin:
There are two electrons => S = s1+ s2 = 0 or 1. S = 0 states are called singlets because they
only have one ms value. S = 1 states are called triplets as ms = +1, 0, -1. There are four
possible ways to combine the spins of the two electrons so that the total wave function has
exchange symmetry.
Singlet (antisymmetric) spin eigenfunction:

Triplet {symmetric) spin eigenfunctions:

Visualising singlets and triplets
Helium wavefunctions:

Total wavefunction for two electrons:

Since total wavefunction must be antisymmetric, Singlet and triplet states therefore
have different spatial wavefunctions

S ms ψspin ψspatial
1
0 0 1/ 2(↑1↓2 −↓1↑2 ) (ψα ( rˆ1)ψ β ( rˆ2 ) + ψ β ( rˆ1 )ψα ( rˆ2 ))
2
+1 ↑1↑2
1 0 1/ 2(↑1↓2 + ↓1↑2 )
1
(ψα ( rˆ1)ψ β ( rˆ2 ) − ψ β ( rˆ1)ψα ( rˆ2 ))
-1 ↓1↓2 2
Electron Correlation
Excited states of He

In absence of e-e interaction the Hamiltonian can be written as

The ground state can be written as

We can use perturbation theory to evaluate

In the absence of e-e interaction the first excited states of the same nl symmetry class are
degenerate

el.(1) el.(2)
Excited States of He:
Since matrix elements between states with different l and ml values vanish we can use
1st order degenerate perturbation theory to get

Since matrix element is independent of ml we can choose ml =0 to evaluate it.

Jnl Represents the electrostatic repulsion between charge distributions corresponding to electrons
1 in definite states and is called the Direct interaction.
Knl represents the repulsion between charge distributions being 50/50 in each state. It arises
purely as a consequence of indistinguishibility and is called the Exchange interaction.

Since and there is a positive energy shift

in the case of singlets and negative in the case of triplets.
Helium terms and Spectra

L S J Term
0 0 0 1S
0

1 0 1 1P
1

2 0 2 1D
2

0 1 1 *3S
1

1 1 2, 1, 0 3P
2,1,0

2 1 3, 2, 1 *3D
3,2,1

Note that singlet and triplet spectra are

essentially independent because of the
selection rule ΔS = 0 for optical
transitions.
The other selection rules are ΔL=±1,
ΔML=±1,0 for electric dipole transitions.
Outline
•Background on EUVL /Current Situation
•Atomic Physics of H atom
•Multielectron Atoms: Alkalis, Helium
•Central Field Model
•Coupling Schemes
•Radiative Transitions, Oscillator Strengths, Selection Rules
•Calculations for Many Electron Atoms, Slater Integrals, Spin Orbit
Matrices etc.
•Photoabsorption
•Statistics Of Levels and Spectra: Compound Atomic States,
Unresolved Transition Arrays
•EUV Spectra of Xe and Sn
•Future directions, Sources at 6.x nm
• Conclusion

–
Wavefunctions for system of interacting particles
 −h 2 Ze 2 e2 
The solutions to the equation ˆ
H iψ i ( rˆi ) =  ∇i − 2
+ ψ i ( rˆi )
 2m 4 πε0 ri 4 πε0 rij 
= E iψ i ( rˆi )

can again be written in the form ψ i ( rˆi ,θ i , φ i ) = Rn i li ( rˆi )Υli m i (θ i , φ i )

The radial wave functions are solutions to d Rn i li 2 dRn i li 2µ  e2 

2

+ + 2 E + Rn l = 0
dri
2
r dri h  4 πε0 ri  i i

and therefore are quite similar in form to for the hydrogenic one-electron functions.
Z eff µe 4
2
Allowable solutions again only exist for where Zeff = Z - σnl.
En = −
(4 πε0 ) 2 2h 2 n 2

Valence electrons are indistinguishable, i.e., not physically possible to assign unique
positions simultaneously. | Ψ( rˆ1, rˆ2 ,..., rˆK , rˆL ,..., rˆN ) |2 =| Ψ(rˆ1, rˆ2 ,..., rˆL , rˆK ,..., rˆN ) |2
This means that multi-electron wave functions must have exchange symmetry:
Ψ( rˆ1, rˆ2 ,..., rˆK , rˆL ,..., rˆN ) = ±Ψ( rˆ1, rˆ2 ,..., rˆL , rˆK ,..., rˆN )

That is, exchanging labels of pair of electrons has no effect on wave

function. As electrons are fermions (spin 1/2), the wavefunction of a multi-
electron atom must be anti-symmetric with respect to particle exchange.
The Central Field, Many Electron Atoms
Partition the Hamiltonian into an independent
particle part and a part that describes the
electron-electron repulsion

Since [H0, L2] = 0 the eigenfunctions

remain characterized by n, l, ml and ms.

Since the effective potential is no longer

exactly Coulomb like, the l degeneracy
for a given l can be removed.
Variation of U (r) with r
Central field approximation
N

Assume V central (ri ) >> Vresidual

i=1

Vresidual can be treated as a perturbation. By writing ψ = ψ1 ( rˆ1 )ψ 2 ( rˆ2 )Kψ N ( rˆN ) we end up
with N separate equations
 h2 2  with E = E1 + E2 + … + EN
− ∇ i − Vcentral (ri )ψ i ( rˆi ) = E iψ i ( rˆi )
 2m 

As potentials only depend on radial coordinate, can use separation of variables:

ψ i ( rˆi ) = ψ i (ri ,θ i , φ i ) = Ri (ri )Υi (θ i, φ i )
where Ri(ri) are radial wave functions and Yi(θi, φi ) are the spherical harmonics
Each electron will therefore have four quantum numbers:
– l and ml: result from solution of Yi(θi, φi ) .
– n: arises from solving radial equation. n and l determine the radial wave function
Rnl(r ) and the energy of the electron.
– ms: Electron can either have spin up (ms = +1/2) or down (ms = -1/2).
For non-interacting particles

What is probability of simultaneously finding a particle 1 at (x1,y1,z1), particle 2 at

(x2,y2,z2),etc.?.
N-particle system is therefore a function of 3N coordinates: Ψ(x1,y1,z1; x2,y2,z2; … xN,yN,zN)
Hˆ Ψ( rˆ1, rˆ2 ,..., rˆN ) = EΨ( rˆ1, rˆ2 ,..., rˆN )
z
Consider the particles as non-interacting, but move in potentials V1 and V2., then:
Hˆ = Hˆ 1 + Hˆ 2 e2 e1
 h 2   h 2 
= − ∇12 + V1 ( rˆ1 ) + − ∇ 22 + V2 ( rˆ2 )
 2m1   2m 2  r2 r1
2
The electron-nucleus potential for helium is Vi = − 2e
i = 1,2 y
4 πε0 ri x

The eigenfunctions of H1 and H2 can be written as the product: Ψ( rˆ1, rˆ2 ) = ψ1 ( rˆ1 )ψ 2 ( rˆ2 )

Hˆ Ψ( rˆ1, rˆ2 ) = ( Hˆ 1 + Hˆ 2 )ψ1 ( rˆ1 )ψ 2 ( rˆ2 )

= (E1 + E 2 )ψ1 ( rˆ1 )ψ 2 ( rˆ2 )

Thus: Hˆ Ψ( rˆ1, rˆ2 ) = EΨ( rˆ1, rˆ2 ) where E = E1+E2

N
For N-particles, E =  Ei
i=1
Self Consistent Field Method

To estimate U(r), The Variational ground state energy is

We must minimise E subject to some constraint

This constraint is imposed using a set of Lagrange Multipliers such that :

This yields the Hartree Equations:

Variation gives:

Thus:
Self Consistent Field Method

To fix the Lagrange Multipliers we multiply the Hartree eqns by and integrate

From this we find that:

It is useful to define a spherically averaged Ui(r):

Hartree- Fock Method

Allows for indistinguishability of electrons by using Slater Determinant Functions

denote N single particle wavefunctions, where

Variational Analysis leads to the Hartree-Fock Equations with an additional

Exchange contribution
Some Conclusions: