Quantum theory and atomic

spectroscopy
Lecture 4
Spin
 The story so far….
• Atomic subshells are made up of
sublevels, which we label with the
quantum number ml
• The number of sublevels is given by 2l + 1
• ml is a manifestation of the space
quantization of angular momentum
• The number of electrons in each sublevel
is limited to just 2
• Now read on …
 Today’s question is……
• Why can a sublevel only hold a maximum of two
electrons?
• Why did Stern and Gerlach see just two spots in
their space quantization experiment?
• By the end of this lecture, we will understand
atoms like helium a little better…..
Bohr’s model of the atom
• Bohr based his famous paper on the idea
that discrete energy levels existed in atoms
(proved it for hydrogen)

• Spectral lines are transitions between

different energy levels- important! He
calculated the energies!

• Franck and Hertz quantified the relationship

between mercury lines and “excitation”
electrons in cathode ray tube
 The Bohr Festival: Discovery of
hafnium
• Bohr claimed chemists believed
unknown element 72 must be
rare – earth
• He predicted it wouldn’t be
• Coster and Hevesy find it is a
transition metal! Named
hafnium in honour of Bohr!
• But… was he really so brave?
Ask Bury!
• Bohr was wrong though about
the subshells- no proper
understanding of the subshell
ordering then
 The crisis of 1922
• (1) Bohr’s model actually predicted the wrong levels, but
since no one understood the ordering of the levels no-
one knew how to fix it
• (2) The old theory was hopeless at explaining the
spectrum of helium, which is a bit worrying as it only has
two electrons
• (3) The spectrum of sodium, with its doublet of lines and
anomalous Zeeman effect could not be explained
• All this was solved by a single new type of angular
momentum
• Now read on …
Spectra of many-electron atoms
• 1919- Kossel-
Sommerfeld laws of
displacement and
interchange
• Odd electrons-
doublet spectra
• Even electrons-
singlet and triplet
spectra
• Explanation next
year!
 The Aufbau principle
• This is a set of empirical rules (1925) for
determining the ground electronic state of an atom
• 1) We fill an atom lowest energy levels 1st
2) For each n, there are n subshells (l)
3) In general, the higher n, l the higher the energy
4) For each l, there are 2l + 1 sublevels
5) Only a maximum of 2 electrons share n, l and
ml
• The latter is the result of the Pauli exclusion
principle “No two electrons can have the same 4
quantum numbers” – yeap, Pauli made up a new
number!
Order of orbitals
• The order of the
relevant sublevels
does depend on the
atomic number
• At high Z, the
subshells do group
according to the
quantum number n
• This is due to
electron- electron
interactions
 Explaining the periodic table

• We can explain the arrangement of elements in terms

of filling subshells
• Add Pauli exclusion principle! But what was the 4th
quantum number?
That crazy Stern-Gerlach result
• In silver there is just one
valence electron – an s
electron
• Therefore, its orbital angular
momentum is zero!
• We should get one spot, not
two!
• Is the fact the electron is
unpaired significant?
 Goudsmit and Uhlenbeck

• They weren’t the first, but their timing was good!

• They suggested an electron has an intrinsic
angular momentum- called spin
• It is a new type of angular momentum!
 Electron spin
• Spin can take half-
integer quantum
numbers
• Thus this is the
missing number Pauli
was looking for!
• An electron can either
spin up or down!

So can state Pauli exclusion principle as

“No two electrons can have the four same numbers
n, l, ml and ms”
 Hund’s rule
• We need this when dealing with partially filled
subshells with l > 0
• Only applies to ground electronic term of an
atom
• Maximise the spin of unpaired electrons to
minimise the energy
• There is no simple explanation- leave it till
next year!
Why do electron’s have spin?
• Young physicist Dirac decides to
solve spin problem
• He tries to combine quantum theory
with special relatively
• Derives Dirac equation and shows all
fundamental particles MUST have
spin! And it must be ½!
• Equation also predicts the existence
of antiparticles
• 1932- anti-electron discovered!
 Total atom spin
• Just like orbital angular momentum, add
all the electron spins to find the total, S

n
S = ∑ si
i

• For a closed shell, the total spin is 0

 Term Symbols
• You need to know the
configuration as you
need (a) total L and
(b) total S
• Electronic term
expressed as
2S+1L 2S
2S++11==multiplicity
multiplicity
e.g gnd state silver is
2S
It also explains the Stern- Gerlach result with silver (Fraser)!
 Term Symbols in spectroscopy
• We represent transitions in terms of Term symbols not individual
electrons
• The energy states of atoms are determined by all the electrons in the
atom and labelled
2S+1L

• States with same configurations are labelled numerically, from lowest

in energy to highest e.g.

12S is lower in energy than 22S

• A transition is often represented in this manner

32P → 22S

with the highest energy state on the left

 Term Symbol test
• Write down the Term symbols
for the following electron
configurations?
• (a) d1p1
Answers will be posted on
• (b) s2p1 the web!
• (c) f14 s1
• Write down (a) the value of L
and (b) the value of S for the
following term symbols
2S
5D
2P
6G
 Spin and selection rules
• In light atoms, there is
a spin selection rule in
optical transitions ∆S =
0
• We can analyse the
calcium atom as a two
electron system
• Poor transitions are
good for atomic clocks!
 Many – electron atoms

• The degeneracy of hydrogen levels is lost

• This is the result of electron – electron interactions we
now call electron correlation
Great! Let’s consider helium….
 The helium atom
• Significant differences
between helium and
hydrogen spectra
• Firstly, we seem to have
two sets of energy levels!
• They correspond to
different values of total
spin
• At one time, thought to be
two forms of helium!!!!
• Secondly, orthohelium
energy levels much
lower!

This last point couldn’t be fully explained until the discovery of quantum mechanics!
Answers to the earlier questions..
• There are two spots in the
Stern- Gerlach experiment
because the valence electron
in silver carries only spin
• The spin of an electron is ½
• Pauli exclusion principle
limits 2 electron to an orbital
• Stern – Gerlach is always a
test of space quantization
(sublevels)
 Hang on……

• Where do these quantum numbers come from?

• Why is angular momentum and energy in atoms
quantised?

• Next time, we will see that one completely new

concept can explain all!