Module 113- Quantum theory and atomic spectroscopy

LECTURE 5 – wave particle duality

12. Einstein and De Broglie

To understand where these 4 quantum numbers come from, and the total change in perception of what electrons
are that ultimately explains n, l , ml and ms , we first need to go back a bit to see what developments were going
on in the understanding of light.

To solve the problem of black body radiation, Planck had introduced the idea of quantized oscillators. These
were material objects, embedded in a blackbody source, which could only absorb or emit radiation of the particular
frequency. Albert EINSTEIN went one step further than this- he believed that light itself was quantized. He
believed that radiation was divided into fundamental, indivisible units called photons (actually, it was G.N.
LEWIS, the chemist famed for his acids and bases that gave them this name- Einstein used “light quanta”). He
used this idea to explain the photoelectric effect- the ejection of electrons from metals when exposed to radiation,
which is characterised by the following:

1) No electrons are ejected, regardless of the intensity of the light, unless the radiation frequency exceeds a
threshold value.
2) The kinetic energy of the electron varies linearly with the frequency of the light, regardless of intensity
 3) Even at low light levels, electrons are ejected immediately if the frequency exceeds the threshold value

I always think that (3) is simply a pedantic extension of (1), but that’s just my opinion. It was our old friend Lenard,
as ever following on from stuff Hertz had done, who carefully documented this behaviour. He didn’t know why this
happened and frankly why did he care as he received the 1905 Nobel Prize anyway? Luckily for us 1905 was the
same year Einstein wrote a paper on quantised light that was to explain the whole thing in a rather simple way.

Einstein was making a crucial conceptual leap over Planck by suggesting that the electromagnetic field was itself
composed of quanta of light. In his paper, he hypothesised what would happen if light really was like this and
considered a number of ramifications including, at the very end, a suggestion that the photoelectric effect could
simply be the result of individual collisions between these light-quanta and electrons. In this case, and if
conservation of energy is obeyed at the microscopic level, then the energy of the photoelectron can be calculated
from

½ m e v 2 = hν − φ (5.1)

The LHS is obviously the electron kinetic energy, hν is the photon energy and φ is a characteristic of that
particular metal known as the workfunction.

Actually, Einstein was not the first to believe light had particle-like properties. Issac NEWTON, for one, believed
in the so-called corpuscular theory of light. But by the end of the 19th Century, experiments on interference and
diffraction of light (including the famous “Newton’s Rings” which was performed by his arch rival Robert HOOKE
to rubbish Newton’s corpuscular theory) seemed to be incompatible with a corpuscular theory for light- it had to be
a wave. What Einstein was proposing was not a return to Newton but that light could show behaviour that was both
wavelike and particle like. Einstein, however, could not explain how.

What I must make clear is that the photo-electric effect is not conclusive proof that light is quantised and there
were other ways to explain this effect. But this photon model was a very elegant solution (at least mathematically)
and needed to be taken seriously. Many scientists, however, were appalled by this idea on a conceptual level,
particularly Neils Bohr, because everyone knew light was a wave, not some fancy particle. The theoretical
argument could have gone on forever, but thankfully some experimentalists moved in: Robert MILLIKEN was
dead against the theory, but he was pretty convinced by 1916 that light was quantised and other evidence began
to pour in that Einstein was onto something (though it has to be said that many believed the maths but not a
photon’s actual existence!) Bohr wasn’t going to give up that easily, and even favoured ditching the conservation of
energy at the microscopic level rather than accept light-quanta (and he did in a truly bizarre theory in 1924 with
Hendrik KRAMERS and John SLATER)! In January 1925, an experiment by Walther BOTHE and Hans
GEIGER had proved that conservation of energy did take place on the microscopic level, so 1 –0 to
Einstein. This was probably the last time Einstein got one over Bohr and they would famously clash over the
meaning of quantum mechanics many years later.

Concurrent with the proof of a quantised electromagnetic field, Louis DE BROGLIE was studying the
ramifications of Einstein’s relativity theory and was coming to some rather dramatic conclusions. De Broglie was
convinced that light quanta had mass, albeit very small (scientists today don’t think so, but they could be wrong, it
won’t be the first time). From this hypothesis, a natural line of thought is this: if light can have a mass and behave
like a particle, can a particle behave like a wave?

Why did he believe light can have a mass? Well, Einstein’s relativity theory has a nice compact equation for the
momentum of light,

E
p = (5.2)
c

where p is the momentum of the wave, E is the total energy of the radiation and c is the speed of light. Evidence
for “light pressure” was as old as the hills: Johann KEPLER noted in 1619 that light pressure was the cause of
comet tails (though its not the only, or most significant, reason for this) and today we know that it is a major factor
in the distribution of micron-sized particles in the Universe. For an individual light quantum, Einstein’s equation can
be combined with the Planck equality E = hν , so

hν h
p = = (5.3)
c λ

De Broglie proposed that if light (which is obviously a wave) can carry a momentum then a particle (which
obviously carries momentum) can also possess a wavelength. This formed the basis of his thesis, which he
completed in 1924. No one had ever postulated a wavelength for material particles before, and if material objects
could then why had this never been detected? Let’s consider a snooker ball rolling on a table at 10 ms-1 and having
a mass of about 0.1 kg, its momentum is 1 kg m s-1. Using equation (5.3) we then find

h 6.626 x10 −34 Js

λ = = = 6.626 x 10-34 m
p 1kgms − 1

This is incredibly small, so its not surprising it had gone unobserved. Remarkably, the state of the art experimental
tools in 1925 could be tuned to detecting the de Broglie wavelength, but you needed to focus attention on the
lightest particle then known- the electron. Consider an electron accelerated by a potential difference ∆φ . The final
kinetic energy of the electron (assuming it starts from rest) is given by

p2
= e∆φ (5.4)
2m e

where e is the charge on the electron. Rearranging the above the formula we get

p = 2me eΛφ

with a potential of 100V, p = 5.37 x 10-24 kg m s-1 e.g. much smaller than a snooker ball. The corresponding de
Broglie wavelength is consequently λ db = 1.2 x 10-10 m or 120 picometers (pm).
This is very small still but it is comparable with the wavelengths of X- rays. Discovered by Wilhelm RONTGEN in
1895, the ability for X-rays to be diffracted when passed through a crystal was hypothesised by Max VON LAUE
in 1912 because their wavelength matched the separation of atomic planes in the crystal. This led to the technique
of X-ray diffraction which was in wide spread use in 1925. What de Broglie was suggesting was that electrons
could also be diffracted by a crystal because of their comparable de Broglie wavelengths.

By the end of 1925, two crucial experiments had demonstrated this phenomenon: one by the Americans Clinton
DAVISSON and Lester GERMER, and the second by George THOMSON in Aberdeen, who passed
electrons through a thin gold foil. The two images below are almost identical, but one was taken using X-rays and
the other by using electrons. The rings are a tell-tale indication that diffraction has taken place. A pretty convincing
demonstration of wave particle duality don’t you think (the answer you are looking for is yes).

There is a delicious irony here. Consider two crucial experiments in the investigation of electron properties:

1) Demonstration that electron is a particle – J.J. Thomson (Nobel Prize 1906)

2) Demonstration that electron is a wave – Sir G. Thomson (Nobel Prize 1937)

The surnames are no coincidence- they were father and son.

The ramifications of wave-particle duality are profound. It not only explains how it is electrons can be diffracted, but
it ultimately leads to the very explanation of the structure of atoms. But first, one of the genuinely earth shattering
results of quantum theory!
13. What wave-particle duality implies part 1: Heisenberg

Werner HEISENBERG discovered his famous uncertainty principle almost by accident while trying to solve a
problem concerning a special class of vibrational motion. Yet it is really just a logical extension of de Broglie’s
wave-particle duality concept. Imagine a simple sine wave. This has a fixed wavelength, and therefore if were light
or an electron it would have a fixed momentum. But can we talk about the position of such a wave. Not in 1-
dimension we cannot- it simply extends all the way to infinity.

Now lets add some waves of different wavelengths (and therefore different momenta). We initially get simple beat
notes but as we pile more and more waves on top, we begin to form a wavepacket. This is localised in space (see
below). It will be moving, but at any time we can identify the approximate location of this “pulse”.

If we continued adding more and more waves, the pulse will eventually collapse into an infinitesimally short pulse,
like a sharp spike. Hence, we know exactly what its location is. But to achieve this we have added an infinite
number of waves with every conceivable wavelength and hence momentum. In other words, now we know the
pulse location, but we have no idea what its momentum (wavelength) is.

If this spike is now a material object, we can see that

“It is impossible to specify simultaneously, with arbitrary precision, both the momentum and position of a
quantum particle”

Heisenberg expressed this in mathematical terms as

 h
∆ p x ∆x ≥ (5.5)
2

∆p x is strictly speaking the root mean square deviation of the momentum from its mean value (i.e the precision)
parallel to the x-axis. So we can simultaneously measure both the location of the quantum object along the x-axis
and the momentum parallel to the y- or z axis with whatever precision we can achieve and not be restricted by the
Heisenberg Uncertainty Principle.

Heisenberg went on in a later scientific paper to expound a further general rule that the quantum theory should
only deal with quantities that can be determined and observed in principle- the so-called observables.

Heisenberg realised that the uncertainty principle would not only apply to just position and momentum, but other
pairs of observables as well. These we call complementary observables. Many properties concerned with
angular momentum, for example, are complementary observables.

This only turned about 200 years of Physics on its head: classical mechanics loved using trajectories to describe
particle motion – but this requires that you simultaneously know both the position and the velocity (and therefore
momentum) of an object which wave-particle duality claims is impossible (to arbitrary precision)!

14. What wave-particle duality implies part 2: Schrödinger

De Broglie’s thesis sparked a new interest amongst physicists about the nature of material things and what we can
understand about the world around us. Sound’s profound? Well, it was probably one of the most crucial discoveries
of the 20th Century, along with the absolute speed limit (that of light, c) and the understanding of how DNA encodes
the message of life.

In our quest to understand atomic quantum numbers, it is the work of Erwin SCHRÖDINGER that provides the
solution we have been looking for. To understand what it was he achieved during six weeks in 1925-1926, we can
do a lot worse than simply look at the abstract to the first of his famous series of papers for the journal Annalen der
Physik (published March 1926)

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 (my italics).

By that final statement he meant the entirely classical wave phenomena of standing waves, where only certain
discrete frequencies are allowed for an individual spring because of the imposition of boundary conditions. The
classic example of this is the standing wave, where the wavelength of the wave is resticted to particular values
because the amplitude of the wave at the boundaries (the fixed points) must have a fixed value (this time, zero).

Only certain so called harmonics can exist, just as in an atom only certain energy levels can exist.
There is a lovely parallel here with the teachings of Greek philosopher and mathematician PYTHAGORAS, who
led a wacky sect in the Greek city of Croton (in Southern Italy) during the Sixth century BCE. Apart from a
fascination with triangles and a disturbing hostility toward beans, Pythagoras believed that the Heavenly bodies
and the Earth were governed by a celestial music, inaudible to humans, known as the music of the spheres.
Everything was the result of musical notes or standing waves: in some ways, it seems he had a point. However,
that is no excuse for being a bean-ophobe.

Quantum mechanics and wave-particle duality can be applied to seemingly simple physical systems but that exist
on an atomic or molecular scale. So the next logical step in our desire to understand the electronic structure of
atoms will be to introduce a quantum mechanical analysis to atoms and in particular the simplest atom of them all,
hydrogen. So the next question is:

• Can we solve the quantum mechanical problem for the hydrogen atom and recover the discrete energy
levels?

Yes we can, but in order to do just that we must first introduce the Schrödinger equation.

Key points in lecture 5

• In quantum theory, there is no fundamental distinction between waves and particles: both display wave-
particle duality.
• All quanta (electrons, photons and the like) possess a momentum that is related to their wavelength. For
traditional particles, this is known as the de-Broglie wavelength.

hν h
p = =
c λ

The wave nature of particles ensures that it is impossible to measure simultaneously the position and
momentum of a particle to an arbitrary precision. This is the Heisenberg Uncertainty Principle.
h
∆ p x ∆x ≥
2

This is a property of all complementary observables.