Quantum theory and atomic

spectroscopy
Lecture 5
Wave-particle duality
 Old quantum theory
• Old quantum theory very good at
describing the microscopic world
• Energy levels of atoms quantized
• Electrons in atoms can be labelled by four
quantum numbers n, l, ml and ms
• n, l and ml take integer values, ms half-
integer
• Add Pauli exclusion principle, Hund’s rule
etc
• BUT …
 The BIG question is……
• Why oh why is this true? Why do we have
quantization? Why do we have these quantum
numbers?
 Classical physics
• Waves- light, sound
• Mechanical disturbance
of medium
• For light- the aether
• Maxwell equations
• No aether found!
• Special relativity (1905)
• Matter- particles, obey
Newton’s laws
 The photoelectric effect

• The kinetic energy depends on wavelength

• The kinetic energy doesn’t depend on intensity
• As soon as light strikes the surface, electrons
appear so long as a minimum frequency is
exceeded
 The workfunction
• We must exceed a minimum frequency (energy)
that is metal dependent which is called the
workfunction
 Enter Einstein
• Albert simply asked the
question: what would
happen if light itself was
quantised?
• Final part of his paper he
suggested it would be a
neat solution to
photoelectric effect
• Imagine individual photons
colliding with electrons!
 Young’s slits
• One problem with the
theory was that it didn’t
seem to explain the
interference of light
• Some thought maybe
this was a statistical
effect
• G I Taylor showed that
interference worked
with very weak light This is still not well understood in
2006!
(one “photon”) in 1909!
So people took a bit of
convincing…
• Milliken checked the experimental
data- nothing wrong there

• Bohr so desperate to keep wave

picture he wanted to drop energy
conservation!

• Bothe and Geiger (1924) finally

demonstrated Einstein probably right.
Light pressure

• This had been understood

for a long time
• Kepler used the idea to
explain comet tails
• However, the momentum
of light is tiny (easily
exceeded by solar wind)
 De- Broglie wavelength
If light can have momentum…
Can particles have a wavelength? h
λ=
E
p
p =
c
hν h
p = =
c λ
This is the mathematical description of WAVE-PARTICLE DUALITY
 An example….
• Consider a snooker ball, mass 0.1 kg and
velocity 10 ms-1

h 6.626 x10 −34 Js

λ = = −1 = 6.626 x 10-34 m
p 1kgms

But if you work this out for ELECTRONS, the

wavelength is similar to X-RAYS
 X- rays
• X- rays discovered by
Rontgen
• 1912 – von Laue
suggested they could be
used to investigate
crystal structure – X-ray
diffraction

If electrons have a wavelength like x-

rays, can we use them in the same way?
Can electrons diffract?

• Yes they can!

• Diffraction pattern
similar to that with X -
rays
• Electrons easier to
use than X-rays
 A wonderful coincidence…
• Electron is particle – J.J. Thomson (NP 1906)
• Electron is wave – G. Thomson (NP 1937)

• Father and son!!!!

 Wave properties
• What is a perfect
sine-wave?
• It has a fixed
wavelength
(momentum)
• But it is infinite in
extent!
• Add more
wavelengths- get beat
notes
Momentum- position
complementarity
• Add more and more
waves to get a
wavepacket
• With enough waves, get a
“spike” localised in space
• But how many waves
have you added? An
infinite number!
• Know the position, don’t
know the momentum
Heisenberg’s Uncertainty Principle
• Werner Heisenberg
suggested this
behaviour would affect
material properties
• “It is impossible to
specify simultaneously,
with arbitrary precision,
h
both the position and ∆p x ∆x ≥
conjugate momentum 4π
of a quantum object”
 Enter Schrödinger
• He wanted to
understand what de-
Broglie’s concept
would mean for
atomic levels
• He got an idea from
an electrical engineer:
find a wave-equation
• In about six weeks he
What he introduced was a new,
had changed science mathematical description of
forever!! small objects he called the
WAVEFUNCTION
 Schrödinger’s wave-equation

In this communication I wish to show that the usual rules of quantisation

can be replaced by another postulate,
in which there occurs no mention of whole numbers.
Instead, the introduction of integers arises in the same natural way as,
for example, in a vibrating spring.

• He was picturing the hydrogen atom as a

series of standing waves!
• Similar to a vibrating guitar string! (But in
3-D)
 Standing waves for dummies
• Create a standing wave
by imposing a boundary
condition e.g. a wall, a
pin or the finger of a
guitarist
• Quantization of
frequencies!!
• For hydrogen, solve its
Schrödinger equation:
do we get quantization?
Answers to the earlier questions..
• The quantum behaviour
of electrons is due to their
wave- particle duality
• This leads to fundamental
changes in behaviour e.g.
Heisenberg Uncertainty
Principle
• The Schrödinger equation
becomes the fundamental
description of nature!
 Alright then……
• What is the Schrödinger
equation and how do we use
it?

• Next time, we will solve it for

a free-particle and meet this
new description of objects:
the wavefunction