The spectra of complex atoms

General Idea
The lines in the spectrum (in either emission or absorption):
•the atom undergoes a transition with a change of energy |ΔE |,
and
•emits or absorbs a photon of frequency
the energies of electrons
in atoms
the actual energy levels:
• not solely the energies of the orbitals
• the energy interaction of the electrons with one another

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Linewidths
A number of effects contribute to the widths of spectroscopic
lines:
•Some contributions to linewidths can be modified by
changing the conditions, and to achieve high resolutions
we need to know how to minimize these contributions.
•Other contributions cannot be changed, and represent an
inherent limitation on resolution.

Doppler broadening
radiation is shifted in frequency when the source is moving
towards or away from the observer.

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 Doppler ….
a source emitting electromagnetic radiation of frequency ν
moves with a speed s relative to an observer, the observer
detects radiation of frequency

Doppler
shifts

nonrelativistic speeds

The detected spectral

‘line’ is the absorption
or emission profile
arising from all the
resulting Doppler shifts.
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•The Doppler line shape is a
Gaussian

•when the temperature is T and

the mass of the atom is m, then
the observed width of the line at
half-height (in terms of
frequency or wavelength) is

to obtain spectra
of maximum
sharpness, it is
best to work with
cool samples.
Doppler
broadening
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 Lifetime broadening
The residual broadening is due to quantum mechanical effects. Specifically,
when the Schrödinger equation is solved for a system that is changing with
time.
If on average a system survives in a state for a time τ (tau), the lifetime of
the state, then its energy levels are blurred to an extent of order δE

Lifetime Heisenberg uncertainty principle >>> uncertainty broadening

broadening

the shorter the lifetimes of the states involved in a transition the

broader the corresponding spectral lines

Lifetime broadening: >>>> finite lifetimes of excited states

•The collisional linewidth is proportional to the pressure
•the natural linewidth of the transition>>> an intrinsic property of the
transition, depend strongly on the transition frequency, low frequency
transitions have smaller natural linewidths than high
frequency transitions.
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 Quantum defects and ionization limits

atomic spectroscopy >>> determination of ionization energies

•the energy levels of a many-electron atom do not in general vary as 1/n2
•the outermost electrons >>>penetration and shielding
•Typical values of Zeff are a little more than 1>>> binding energies slightly lower
than −hcR/n2 >>> quantum defect, δ (purely empirical quantity)
•Energy as −hcR/(n − δ )2

Rydberg states
some excited states that are so diffuse that δ →0 and the 1/n2 variation is
valid

a plot of wavenumber against 1/n2 can be used to obtain I by extrapolation

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 Singlet and triplet states
•Parallel and antiparallel (paired) spins differ in their overall spin angular momentum
•The state of the atom with the spins parallel lies lower in energy than the state in
which they are paired (Hund’s maximum multiplicity rule)
•Both states are permissible, and can contribute to the spectrum of the atom.
Singlet
The paired-spin arrangement denoted σ− (the Pauli principle)
Singlet spin function

Triplet
The state of two parallel spins
The angular momenta of two parallel spins add together to give a nonzero total spin,

Triplet spin functions

for states arising from the same configuration, the triplet state generally
lies lower than the singlet state. 7
SPIN–ORBIT COUPLING
The interaction of the spin
magnetic moment with the
magnetic field arising from the
orbital angular momentum

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The strength of the coupling, and its effect on the energy levels
of the atom, depend on the relative orientations of the spin and
orbital magnetic moments, and therefore on the relative
orientations of the two angular momenta

The total angular momentum

the spin–orbit interaction depends on the total angular
momentum of the electron, the vector sum of its spin and orbital
momenta
•the spin and orbital angular momenta are nearly parallel >>>
the total angular momentum is high
•when the two angular momenta are opposed >>> the total
angular momentum is low.

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The total angular momentum of an
electron:

•the quantum numbers j and mj, with j = l + ½

(when the two angular momenta are in the same
direction) or j = l - ½ (when they are opposed).
•The different values of j that can arise for a given
value of l label levels of a term.
•l = 0, the only permitted value is j = ½ (the
total angular momentum is the same as the
spin angular momentum because there is no
other source of angular momentum in the
atom).
•l = 1, j may be either 3/2 (the spin and orbital
angular momenta are in the same sense) or ½
(the spin and angular momenta are in opposite
senses).
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•The dependence of the spin–orbit interaction on the value of j :
the spin–orbit coupling constant, Ã (expressed as a wavenumber).
•the energies of the levels with quantum numbers s, l, and j:

•The strength of the spin–orbit coupling depends on the nuclear

charge.
•The greater the nuclear charge the stronger the spin–orbit
interaction.
•The coupling increases sharply with atomic number (as Z4).

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 Fine structure
Two spectral lines are observed when the p
electron of an electronically excited alkali
metal atom undergoes a transition and falls
into a lower s orbital.
•One line >> a transition starting in a j =
3/2 level
•the other line >> a transition starting in
the j = ½ level of the same
configuration.
The two lines are an example of the fine
structure of a spectrum, the structure in a
spectrum due to spin–orbit coupling.

Sodium vapour excited by an electric

discharge (for example, in one kind of
street lighting). The yellow line at 589 nm
(close to 17 000 cm−1) is actually a doublet
composed of one line at 589.76 nm (16
956.2 cm −1) and another at 589.16 nm (16
973.4 cm −1)
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Term symbols and selection rules

Term symbol gives three pieces of

information:
• The letter (P or D in the examples)
indicates the total orbital angular
momentum quantum number, L.
• The left superscript in the term symbol
(the 2 in 2P3/2) gives the multiplicity of the
term.
• The right subscript in the term symbol
(the 3/2 in 2P3/2) is the value of the total
angular momentum quantum number, J.

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The total orbital angular momentum
When several electrons are present >>> how their individual orbital angular
momenta add together or oppose each other.

The total orbital angular momentum quantum number, L >>> the magnitude of
the angular momentum through {L(L + 1)}½ħ.
It has 2L + 1 orientations distinguished by the quantum number ML, which can
take the values L, L − 1, . . . , − L.

The value of L (a non-negative integer) is obtained by coupling the individual

orbital angular momenta by using the Clebsch–Gordan series:
The terms differ in energy on account
of the different spatial distribution of
the electrons and the consequent
differences in repulsion between
them.

Term symbols only consider the electrons of the unfilled shell. In the case of a single
electron outside a closed shell, the value of L is the same as the value of l; so the
configuration [Ne]3s1 has only an S term.
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 The multiplicity
Total spin angular momentum quantum number, S, for several electrons

each electron has s = ½

two electrons: S = 1, 0
three electrons: S = 3/2 and S = ½
the total spin angular momentum is obtained by coupling the third spin to each of
the values of S for the first two spins

The multiplicity of a term is the value of 2S+1

a singlet term
all paired electrons, S = 0
1S >>> (as for a closed shell, like 1s2), there is no net spin

a doublet term,
A single electron, S= s = ½,
2S >>> [Ne]3s1
2P >>>[Ne]3p1

a triplet term
two unpaired electrons S = 1, so 2S + 1 = 3
3D
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The total angular momentum
the quantum number j : the relative orientation of the spin and orbital angular momenta
of a single electron.

The total angular momentum quantum number, J : does the same for several electrons (a
non-negative integer or half integer)

a single electron outside a closed shell

J = j, with j either l +½ or | l -½ |.
•[Ne]3s1 configuration has j = ½ (because l = 0 and s =½ ) >>> 2S term has a single
level, which we denote 2S ½.
•[Ne]3p1 configuration has l = 1; therefore j = 3/2 and ½; the 2P term therefore
has two levels, 2P3/2 and 2P1/2. These levels lie at different energies on account of
the magnetic spin–orbit interaction.

several electrons outside a closed shell

•the spin–orbit coupling is weak (for atoms of low atomic number) >> Russell–
Saunders coupling scheme
•effective only when all the orbital momenta are operating cooperatively >>> total L
•all the spins are coupled >>> total S.
•the two kinds of momenta coupling through the spin–orbit interaction to give a total
J. 17
The permitted values of J are given by the Clebsch–Gordan series

3D term of the configuration [Ne]2p13p1, the permitted values of J are 3, 2, 1

(because 3D has L = 2 and S = 1), so the term has three levels, 3D3, 3D2, and 3D1.

L≥S
the multiplicity is equal to the number of levels.
2P term has the two levels 2P 2
3/2 and P1/2, and
3D has the three levels 3D , 3D , and 3D .
3 2 1
L<S
the term 2S, for example, has only the one level 2S½

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Heavy atoms, those with high Z:
•Russell–Saunders coupling fails, the spin–orbit coupling is large.
•the individual spin and orbital momenta of the electrons are coupled into
individual j values; then these momenta are combined into a grand total, J.
• jj-coupling.
•Eg. in a p2 configuration
•the individual values of j are 3/2 and ½ for each electron
•If the spin and the orbital angular momentum of each electron are
coupled together strongly, it is best to consider each electron as a
particle with angular momentum j = 3/2 or ½.
•These individual total momenta then couple as follows:

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 Selection rules
Term symbols:
•Any state of the atom
•any spectral transition the transitions giving rise to
the yellow sodium doublet

The corresponding absorptions

Selection rules
for atoms

a forbidden transition apply when Russell–Saunders

coupling is valid (in light
atoms, those of low Z)

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9.4 Specify and account for the selection rules for transitions in hydrogenic
atoms.
9.8 Describe the orbital approximation for the wavefunction of a manyelectron
atom. What are the limitations of the approximation?
9.10 Describe the physical origins of linewidths in absorption and emission
spectra. Do you expect the same contributions for species in condensed and
gas phases?
9.3(b) When ultraviolet radiation of wavelength 58.4 nm from a helium
lamp is directed on to a sample of xenon, electrons are ejected with a speed
of 1.79 Mm s−1. Calculate the ionization energy of xenon.
9.17(b) A molecule in a gas undergoes about 1.0 × 109 collisions in each
second. Suppose that (a) every collision is effective in deactivating the
molecule rotationally and (b) that one collision in 10 is effective. Calculate
the width (in hertz) of rotational transitions in the molecule.

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