Atomic

spectra and structure:

Bohr model of hydrogen
Atomic structure
Greeks: Indivisible constituents of all matter
J. J. Thomson finds electron
Rutherfords planetary model

Atomic spectra
Bohrs quantized model
Franck-Hertz experiment: Further evidence
of quantization of atomic structure

Atomic structure Brief history

Greeks: Atoms determine
properties of matter
Indivisible constituents

J. J. Thomson discovers electron (1897)

Proposes plum-pudding
model of atom

Atomic structure Nuclear Atom

Geiger-Marsden (Rutherford gold-foil)
experiment (1909)
Demonstrates massive, positively charged nucleus

Rutherford planetary model of atom (1911)

Positively charged nucleus surrounded by negative
electrons

Atomic spectra
Emission and absorption spectra

Atomic'spectra''hydrogen'
Atomic spectra hydrogen
Emission'spectrum'

Emission spectrum
Observe'narrow'emission'wavelengths'according'to'
empirical'formula'(Rydberg'formula)'
Observe narrow emission wavelengths according to
empirical formula (Rydberg formula)
Rydberg'formula'
formula
Rydberg
1
hc
1

= hc
12
R
m
=
R m2

1
n2
n2

1
1

Rydberg'constant'
Rydberg constant

R = 13.6 eV
R = 13.6 eV

Absorp<on'spectrum'
Absorption spectrum

Not'all'lines'of'emission'are'found'in'absorp<on'
Not all lines of emission are found in absorption

Problems with planetary model

Classical treatment predicts
Electron orbiting the nucleus undergoes constant
acceleration and thus should continually emit
radiation
Electron should spiral into nucleus in
approximately microseconds
Radiation emitted
should have a
continuous spectrum
of frequencies

Bohr model of hydrogen

Centripetal acceleration
Electron orbits nucleus in circular orbit
Electron and nucleus bound by Coulomb force

This gives the kinetic energy

1 e2
me v 2
F =
=
2
4 0 r
r

2
1
1
e
K = me v 2 =
2
8 0 r

Potential energy is just Coulomb potential

U=

Total energy is

E=

Classical up to this point. . .

1 e2
8 0 r

1 e2
4 0 r

Bohr model of hydrogen

Bohr postulates:
Electrons can only occupy certain stationary
states, in which radiation is not emitted and
angular momentum is quantized

L = me vr = n~

~ = h/2

Radiation is only emitted or absorbed when

the electron makes a transition from one
stationary state to another.

Bohr model of hydrogen

Solving for velocity

L = me vr = n~ =)

v=

Use this result in force equation

2

1 e
me v
me
F =
=
=
2
4 0 r
r
r

n~
me r

n~
me r

This can be solved for allowed radii

4 0 ~2 2
2
rn =
n = a0 n
2
me e

2
Bohr radius

a0 0.53
A

Bohr model of hydrogen

Allowed energy levels
(sub rn into classical
expression for total energy)
En =

me e4 1
=
2
2
2
2
32 0 ~ n

E1 = 13.6 eV

e2
1
=
2
8 0 a0 n

Same as Rydberg constant!

n is called the quantum number

E1
n2

Emission spectra
Photon energy
given by difference
between initial and
final atomic energy
levels
Eph = Em

ph

En = E1

E1
=
h

1
n2

1
n2

1
m2

1
m2

Absorption spectra
Photon energy
given by difference
between initial and
final atomic energy
levels
Start in ground state at room temperature!

Eph = Em

ph

En = E1

E1
=
h

1
n2

1
n2

1
m2

1
m2

Hydrogen-like ions

Ze

Nuclear charge now Ze

Change all e2 to Ze2 in previous treatment
This gives

a 0 n2
rn =
Z
ph

E1 Z 2
=
h

En =

1
n2

Z2
E1 2
n

1
m2

Franck-Hertz experiment 1914

Further evidence for Bohr model

Measured current drops every 4.9 V

Electrons experience an inelastic collision
and lose 4.9 eV of energy

Limitations of Bohr model

Cannot be applied to multi-electron atoms.
Does not predict fine structure of atomic
spectral lines.
Does not provide a method to calculate relative
intensities of spectral lines.
Predicts the wrong value of angular momentum
for the electron in the atom.
Violates the Heisenberg uncertainty principle
(although Bohr's model preceded this by more
than a decade).

Summary of Bohr model

Start with classical, circular orbits
Angular momentum is quantized in allowed
stationary states

L = me vr = n~
Gives allowed radii and energy levels
4 0 ~2 2
2
rn =
n
=
a
n
0
me e2

En =

E1
n2

Emission and absorption of light by transitions

between stationary states only

Wavelike behavior of matter

Double slit experiment with photons
de Broglie hypothesis
Davisson-Germer experiment
Diffraction and interference with larger
systems: atoms, molecules
Wave-particle duality: Wave function

Double slit experiment revisited

WAVE
At low light levels
interference pattern
requires finite time
to collect light
PARTICLE
Photons detected one at a time at a
localized point!

de Broglie hypothesis
If light has both wave and particle
properties, cannot matter also
have wave properties?
Special relativity implies: E 2 = p2 c2 + (mc2 )2
For a photon:
E = pc
Using the Planck relation: E = h = hc
de Broglie wavelength
dB

h
=
p

de Broglie waves?
de Broglie went beyond light and
suggested this equation holds
for all matter
h
dB =
de Broglie wavelength
p
Why not observed in everyday life?
m = 0.16 kg
v = 161.26 km/h
~ 44.8 m/s
h
=
cricket
mv
6.626 10 34 Js
=
(0.16 kg)(44.8 m/s)

= 9.2 10

35

m = 92 kg
v = 44.72 km/h
~ 12.42 m/s

h
Bolt
mv
6.626 10 34 Js
=
(92 kg)(12.4 m/s)
=

= 5.8 10

37

de Broglie on Bohr atom

de Broglie looked at Bohrs atomic
model like a musical instrument.
Electrons guided by pilot waves
in each orbit. Orbit circumference = integer
number of wavelengths

2rn = n dB
h
dB =
p

~
pn =
a0 n

Analogy to optics
When does wavelength of matter
wave become relevant?
Similar to diffraction in optics:
When scattering objects (of size d) become
comparable to wavelength
Wavelength

&d

Optics

Matter waves

Ray Optics

Particle
Trajectories

Wave Optics

Wave
Mechanics

Momentum matters
When does wavelength of matter
wave become relevant?
Similar to diffraction in optics:
When scattering objects (of size d) become h
dB =
comparable to wavelength.
p
Electrons with kinetic energy K = 50 eV
can use non-relativistic form of K
since K << mec2 = 0.511 MeV

p
p2
K
=) p 2mK
2m
pc

2mc2 K

p
pc 2(0.511 106 eV)(50) eV

= 7.15 103 eV

hc
1240 eV nm
=
=
pc
7.15 103 eV
= 0.173 nm

Lattice spacing
in crystals

Momentum matters
When does wavelength of matter
wave become relevant?
Similar to diffraction in optics:
When scattering objects (of size d) become h
dB =
comparable to wavelength.
p
Neutrons with kinetic energy K = 0.00024 eV
can use non-relativistic form of K
since K << mnc2 = 940 MeV

p
p
K
=) p 2mK
2m
2

pc

2mc2 K

p
pc 2(940 106 eV)(2.4 10

eV)

= 672 eV

hc
1240 eV nm
=
=
pc
672 eV
= 1.85 nm

Nanowires

Electron diffraction: Davisson-Germer

First direct demonstration of wave
experiment (1925)
properties of matter

Constructive interference

d sin = n
Nickel lattice spacing
d = 0.215 nm

d sin = (0.215 nm) sin(50 )

Electrons accelerated through
potential difference giving
K = 54 eV

h
=
= 0.167 nm
mv

= 0.165 nm
Data and theory in good
agreement!

Double slit experiment with electrons

Two-paths around
a charged wire
(Mach-Zehnder interferometer)

Electron microscopes
used in many
applications
resolution ~ 0.1 nm
A. Tonomura, et al, Am. J. Phys. 57, 117120 (1989).

Matter-wave diffraction with free-standing

gratings over the years

1961

1999

2012

Jnssen (Cu grating)

Arndt (Si3N4 grating)

Arndt (Si3N4 grating)

Classical uncertainty in beam energy

Spread in electron beam energy leads to

spread in wavelength and thus diffraction pattern

Consider diffraction grating
Constructive interference:

d sin

= n
dB

For small angles:

Fractional uncertainty in
scattering angle

n
=)

Non-relativistic momentum:

2mK =)

dp
p=
dK

h
=
p
p
=
p

1
K = (2mK)
2

1/2

h
=
p

Fractional uncertainty
in wavelength equal to
that of momentum

1
2m K = p K
2

Classical uncertainty in beam energy

Spread in electron beam energy leads to

spread in wavelength and thus diffraction pattern

Consider diffraction grating
Constructive interference:

d sin

= n
dB

For small angles:

Fractional uncertainty in
scattering angle

n
=)

h
=
p

p
1 K

=
=

p
2 K
Eph
=
Eph

h
=
p

For non-relativistic matter

For a photon (note factor of 2 difference)

Summary: Diffraction and interference

of matter waves

Interference of matter
waves

Electrons
Neutrons
Atoms
Molecules

de Broglie wavelength
dB

h
=
p

Bragg scattering
Double slit
Diffraction grating

C60
Phthalocyanine

Spread in kinetic energy of particles leads to

spread in diffraction angle!
1 K
=
2 K

Eph
=
Eph

Wave-particle duality
Double slit (again)
Superpostion
Wave function
Probability
Complementarity
Uncertainty principle

Double slit interference

Detection of a particle at point x on the screen
governed by interference of pathways the
particle could take (Feynman)
Two possible paths (r1 or r2), with equal
amplitudes A, and phases 1 and 2
1 = kr1 =

2 = kr2 =

d
L + x+
2

2 !1/2

2 !1/2

L + x

d
2

Double slit interference (Superposition)

Particle flux (number per unit time) at a point
x on the screen is given by the total amplitude
squared
2
N = |Atot |

Atot = A1 + A2 = A(ei
N = A2 |ei

+ ei 2 )

+ ei 2 |2 = 2A2 (1 + cos(

= 1

2xd
2
L
2

N (x) = 4A cos

xd
L

))

Double slit with which-path

information

Look to see through which slit the electron passes

(put a wire loop around each slit)

Any knowledge of which slit localizes the

particle and destroys the superposition of
possible paths hence no interference.

Complementarity
Wave or particle? You decide! Depends on
how you look at the system
Wave nature of system can be observed when
performing a wave-like experiment
Particle nature of system is observed when
performing a particle-like (which-path)
PARTICLE
experiment
WAVE

Wave-particle duality
Wave wave function, e.g. a plane wave
(x, t) = Aei(kx

t)

Well-defined wavelength (frequency or energy)

and momentum
Completely delocalized (no spatial or temporal
information)

Particle trajectory

x(t) =

v(t0 )dt0

Well-defined position
Wavelength (and therefore momentum)
undefined
In nature both wave and particle properties are present until you look!

Wave-function interpretation
Born interpretation: Wave function describes
probability to find particle in a small region
about x at time t
2

P (x)dx = | (x, t)| dx

Superposition and wavepackets

Adding two or more plane waves gives a beat
frequency and localized wavepacket

sin(k1 x) + sin(k2 x)

10
X

m=1

sin(km x)

Superposition and wavepackets

Adding two or more plane waves gives a beat
frequency and localized wavepacket
Taken to a continuum sum -> integral
Gaussian wavepacket
(x) =
| (k)|2
k
p
2

(k)e

ikx

dk =

1
1

k2 /2 k2 ikx

dk

1
ax2 +bx

dx =

1/2
a

exp

b
4a

Superposition and wavepackets

Adding two or more plane waves gives a beat
frequency and localized wavepacket
Taken to a continuum sum -> integral
Gaussian wavepacket
(x) =
| (k)|2
k
p
2

1
1

(k)e

ikx

dk =

k2 /2 k2 ikx

dk

(x) = p e
1
x= p
2 k

x2

k2 /2

Superposition and wavepackets

Adding two or more plane waves gives a beat
frequency and localized wavepacket
Taken to a continuum sum -> integral
Gaussian wavepacket

x k = 1/2
| (k)|2
k
p
2

px = ~k

~
x px =
2

1
x= p
2 k

Heisenberg uncertainty principle

Position and momentum are not
simultaneously well-defined

~
x px =
2

p = ~k
x k = 1/2

Single slit or confined particle: Example

electron confined to an atom
x 0.5
A
Gives nearly the same energy as the
ground state energy of hydrogen!

(pc)2
(~c)2
E=
=
= 15 eV
2
2
2
2mc
2 x mc

~
p
x

Wavicles summary
Wave function describes de Broglie waves
(x, t) = A(x, t)ei (x,t)
Wave function describes probabilities where one
will find a particle
P (x)dx = | (x, t)|2 dx
Superposition key
Superposition of plane waves leads to localized
wavepackets
Measuring position collapses superposition
Complementarity Can only observe wave or particle
nature in a given experiment

Heisenberg Uncertainty Relation

x p=h