14: ELECTRONIC SPECTROSCOPY

TERM SYMBOLS FOR DIATOMIC MOLECULES

2S+1

|ML| g/u

|ML| = molecular angular momentum

(replaces atomic L)

2S+1 = spin multiplicity (same as atoms)

g/u = total inversion symmetry for homonuclear diatomic molecules
Must have inversion symmetry, so cannot specify with heteronuclear diatomic molecules
Similar to the term symbols used for atoms
Atomic term symbols based on looking at combination of electrons in partially filled orbitals.
Similarly, each electron in an MO has spin and orbital momentum associated with it
Molecular term symbols look at all the possible combinations of spin and z-axis orbital
momentum for electrons in the highest-occupied degenerate sub-shell MOs.
E.g., all possible combinations of 2 electrons in O2 molecule occupying two degenerate
1g MOs.
Atoms
2S+1

Term Symbols
Orbital Momentum
- along z axis

- total

LJ

Molecules
|ML| g/u

2S+1

Choice of z axis is arbitrary for

spherical atom
ml = component along z axis for
individual electron
ML = ml,i

z-axis defined as
internuclear axis, po
ml = component along z
axis for individual
electron
ML = ml,i
|ML| = 1: (s = sigma)
2: (p = pi)
3: (d = delta)

L = 1:
2:
3:
ML = L,

Electron Spin
- along z axis
- total

ms =
MS = ms,i

L not fully applicable for

molecules due to lower
symmetry of molecules
(not spheres)
ms =
MS = ms,i

Ms = S, S-1, ... S
Spin multiplicity = 2S+1

Ms = S, S-1, ... S
Spin multiplicity = 2S+1

Total Combined
Angular Momentum

J=L+S
J = L + S, L+S-1, |L-S|

Inversion Symmetry

Gentry, 2013

S
P
D
L-1, ... 0 ..., L

If inversion symmetry
exists:
gi *gj = g,
gi*uj = u, ui *uj =g

REMINDER ON HOW TO CONSTRUCT ATOMIC TERM SYMBOLS

EXAMPLE: One electron in a 2p orbital (2p1)
A) Map all the possible microstate combinations of sub-orbitals and spins.
For the 2p1 example:
2p orbitals can be 2px, 2pz, or 2py (ml = -1, 0, or 1)
For an electron in each sub-orbitals, the spin can be up (+ ) or down (- )
Thus, there are a total of 6 possible microstates as shown below.
2p

ml= +1
ml= 0
ml= -1

B) For each microstate, add each electrons mS to get total Ms for the atom
and similarly add each electrons ml to get Ml
For the 2p1 example:
There is only one electron for each microstate.
Therefore summing over all electrons in the microstate is a trivial exercise
Ms=ms

Ml= ml

-1

+1

-1

+1

C) Back-calculate using allowed values of Ms to find S and similarly Ml and L.

Allowed ML values = L, L-1, ..., L
Allowed Ms values = S, S-1, ..., S
For the 2p1 example:
Ml = +1, 0, of -1, therefore only way to have these Ml values is if L = 1
Ms = + or , therefore only way to have these Ms values is if S = +
Spin multiplicity = 2S+1 = 2
D) Find total angular momentum, J, by combining S and L values
J = L+S, L+S-1, |L-S|
For the 2p1 example:
Maximum value of J = L+S = 1 + = 3/2
Minimum value of J = |L-S| = 1 =
No room for additional values between J = 3/2 and 1/2 .
E) Form atomic term symbol and calculate spin-orbit coupling
2S+1
LJ
EL,S,J = hcA {J(J+1) L(L+1) S(S+1)} A = spin-orbit coupling constant
For the 2p1 example:
2
State 1: P1/2 , E1, , = hcA {3/4 2 3/4} = - hcA
2
State 2: P3/2 , E1, , 3/2 = hcA {15/4 2 3/4} = + hcA

Ch 14: Electronic Spectroscopy

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CONSTRUCTING DIATOMIC MOLECULAR TERM SYMBOLS

Similar Steps to Atomic Term Symbols
A) Construct all possible microstates
ml = angular momentum along z axis for individual electron in molecular orbital
Atomic orbitals have complete set of ml values along z axis for a given l value
ml = +l, +l-1, ..., -l
HOWEVER
Molecular orbitals, on the other hand, do not use a complete set of ml for given MO
Symmetry of molecule means that not all atomic sub-orbitals contribute to a set of
degenerate molecular orbitals.
EXAMPLE: diatomic molecules
Atomic 2p orbitals (l=1) have ml =+1,0,-1 corresponding to 2px, 2pz, and 2py
But molecular orbitals either formed by mixing 2s and 2pz (=2po) to form MO
Or mix 2px and 2py (formed from 2p-1 and 2p+1) to form MO.
The set of possible allowed microstates must reflect these symmetry considerations
B) Add up the individual ms and values to find MS and
MS = ms,i
ML = ml i
C) Use allowed values of MS to find S
Allowed Ms values = S, ..., +S
D) L is no longer a true quantum number due to lack of spherical symmetry in a molecule
(atoms on the other hand do have spherical symmetry)
However still use same methodology to identify L for term state
Allowed ML values ~ -L, ..., +L
Hence identify set of ML values associated with a given maximum |ML|
For maximum |ML| = 0,1,2,3 have
|ML|max = 0 (s= sigma)
|ML|max = 1 (p = pi)
|ML|max = 2 (d = delta)
E) For molecules having inversion symmetry, find total g or u symmetry
Multiply the symmetry element for each electron (1 and 2) in the MO
g1*g2 = g, g1*u2 = u, u1*u2=g
I.e. follows multiplication rules as if each g=+1 and u=1
F) Term symbol =

Ch 14: Electronic Spectroscopy

2 S +1

ML

g /u

-3-

Example 1: H2
MO configuration: 1g2

H2

1u

1s

1s
1g

Spin:
All electrons paired, therefore # spin up equals # spin down; and MS=0
1g (ml=0)
(1s atomic orbitals each have ml=0)

0
MS = ms
If MS = 0, then S=0
z-component Angular Momentum:
molecular orbital, therefore only ml = 0 atomic orbitals can contribute
|ML| = sum of individual ml = 0 (L=0 means s for atoms, so for molecules = )
Inversion symmetry g/u
H2 has inversion symmetry, thus g/u notation is applicable
Electron #1 is in g MO, and electron #2 is in g MO, therefore g1 * g2 = g
Term symbol:

Example 2: H2
MO configuration: 1g2 1u1
1g2 is fully occupied so does not need to be considered
1u1 is partially occupied with a single unpaired electron
Spin:
1g
Can ignore fully occupied 1g orbital
1u (ml =0)

MS

-
MS = S, S-1, ..., -S
Therefore S = and spin multiplicity = 2S+1 = 2
z-component Angular Momentum:
Electron is in a orbital made up of 1s atomic orbitals, so ml =0 for that lone electron
Therefore |ML| = 0 ()
Inversion symmetry g/u
H2- has inversion symmetry, therefore g/u is applicable
The one electron in an unfilled suborbital is in a u orbital, therefore total g/u
symmetry is u.
Term symbol:

Ch 14: Electronic Spectroscopy

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Example 3: O2
Ground state configuration: 1g21u22g22u23g21u41g2
All sub-shells fully occupied except the antibonding HOMO, 1g2
O2 has two degenerate 1g orbitals, which are partially occupied with 2 e-s
Furthermore, MOs can only have AO contributions from 2px and 2py (ml = +1 or -1)
ml = +1

2p ml = 0
ml = -1

M s = ms
|M L| = ml

+1

-1

-2

+2

Scenario 1: 2 Electrons in Separate g Orbitals

Angular Momentum: one electron in orbital made of p-1 atomic orbitals ml = 1, and
other electron in orbital made from in p+1 atomic orbitals (ml = +1)
... therefore |ML| = (+1) + (-1) = 0 (L=0 is s for atom so for molecule = ).
Spin: Since the electrons are in separate MOs, they can have spin in either the same or
opposite direction

MS
1
0
0
-1
MS = S, S-1, ..., -S
Therefore S = 1 (MS=1,0,+1) or S = 0 (MS=0)
g/u symmetry: the two electrons are both in g orbitals
g1 *g2 = g
Term Symbol: Electrons in separate 1g orbitals can be in one of two term states
3

g (spins aligned to give triplet state)

... or 1g (spins in opposite direction for singlet)
Scenario 2: 2 Electrons in Same g Orbital
Spin: Since electrons in same orbital, they must have opposite spin

MS
0
Therefore S=0
Angular Momentum: If electrons in same g orbital
ml 1 = ml 2 = 1
... and therefore |ML| = 2 ( L=2 means d for atoms, so for molecules = ).
g/u symmetry: The two electrons are both in g orbitals
g1 *g2 = g
Term Symbol: 2 electrons in the same 1g orbital gives
1
g

Ch 14: Electronic Spectroscopy

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SPIN-ORBIT COUPLING
Atomic term states lead to spin-orbit coupling
EL,S,J = hcA {J(J+1) L(L+1) S(S+1)} A = spin-orbit coupling constant
Caused by magnetic interactions of orbital angular momentum and spin angular
momentum
Similarly, molecular term states give rise to splitting of otherwise degenerate sub-orbitals.
However, due to complexity of MO energies, there is no simplifying expression for spinorbit energy like there is with atomic term states
For O2 1
g2 sub-orbitals:
To first approximation the two anti-bonding MOs are degenerate
But with spin-orbit coupling from the two electrons, there is a splitting of energies for the
different term states
Term
State
3
g
1
g
1
g

Relative Energy
(cm-1)
0
7,882
13,121

Ro
(pm)
120.7
121.6
122.7

(cm-1)
1580
1509
1433

from Atkins, pg 483

Energy

O2

1
g2 Occupancy
with spin-orbit coupling

2u

1g

2p

2p

1u

2g

1u
2s

2s
1g

Ch 14: Electronic Spectroscopy

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SELECTION RULES FOR ELECTRONIC TRANSITIONS

|ML| = 0, 1
Therefore and are allowed transitions, but is forbidden
S = 0
Change in spin multiplicity such as singlettriplet means that an electron would have to
change the direction of its spin, and not just its orbital and energy level.
g u,
Must change inversion symmetry between initial and final state... if inversion symmetry
exists.
Rule is a result of transition moment integral f i d

acts like x, y, or z axis, therefore has u inversion symmetry

Only way integral can be non-zero is if overall integrand has even symmetry, g
Odd symmetry, u, would mean positive coordinates would cancel negative
coordinates
For gu: u u g = g 0 but for gg: g u g = u = 0
None of these selection rules are absolute, since all have built in assumptions.
But forbidden transitions are much weaker and take much longer to occur.

Ch 14: Electronic Spectroscopy

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FRANCK-CONDON PRINCIPLE
Because nuclei are much more massive than electrons, transitions between electronic
states occur at a much faster rate than the nuclei can respond.
Background
Ground electronic states and excited electronic states all generally follow a Morse
potential dependence of energy vs. nuclear separation distance, r.
However, the equilibrium separation distance often differs from one electronic state to
the next depending on the atomic orbitals that contribute to the specific MO.
... and the width of the potential well also differs for the two states (giving rise to
different spring constants and vibrational frequencies)
Oxygen Bond Lengths of Molecular States
Ground State

Excited State

X 3 g -

2
u

1*g

A 3 u+

Bond Order
=2
Bond Length
= 120pm

2
u

Bond Order
=1
Bond Length
= 150pm

1*g

1u

1u

2
g

2
g

A molecule undergoing an electronic transition to an excited state will redistribute its nuclei
to reach its new excited-state equilibrium geometry.
But the Franck-Condon principle says that this re-positioning of nuclei is MUCH
SLOWER than the actual electronic transition between states.
Therefore the electronic transition is assumed to occur at the initial, ground-state
equilibrium position, with any re-positioning of the nuclei occurring at some later
time.
Franck-Condon Principle
1) Separation distance remains
constant during electronic transitions
2) Later moves to new equilibrium position

Separation distance does

NOT change during transition

ro,i ro,f

ro,i ro,f

Ch 14: Electronic Spectroscopy

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Franck-Condon Simplification
Formal solution requires calculating the transition dipole for various vibronic transitions.
if = *f i d
where i and f each are combinations of electronic and vibrational wave functions
BUT Because of the fixed nuclear distance during transition, it is possible to construct a
simplified model for transitions to excited vibrational states.
An electronic ground-state molecule will likely sit in its ground-state vibrational state since
vibrational energies are usually much larger than available thermal energy.
The position of this ground state electron can be thought to be the equilibrium center
position.
When the molecule undergoes an electronic transition, it can transition up to any number of
different vibrational levels in the excited electronic state depending on the energy
of the light.
No longer have v = 1 selection rule for vibrations since going to a different Morse
potential well during an electronic transition.
Given that the nuclear separation distance does not change, the vibrational level in the
excited state with the highest probability of being found at that distance will
be the vibrational state whose potential-energy boundary is at that distance.
That is to say, when averaged over time, vibrations are most likely to be found at the
extremes of the vibration where the atoms slow down and then reverse direction,
rather than at the center of the vibration where the atoms have reached maximum
velocity.
Thus the most likely transition, and the transition having the highest absorbance, will be for
the excited vibrational state whose potential well is bounded at the same distance
as the ground state equilibrium separation.
For the schematic figure below
The molecule begins in the zero vibrational state for the ground electronic state, i.
It undergoes an electronic transition to the f excited electronic state
Since the nuclei do not have a chance to reposition themselves, the most probable
transition will be to the point where the excited potential well for f intersects
with the equilibrium distance for the ground state.
For the diagram below, this intersection occurs at the =2 vibrational level in the
excited electronic state.
The absorption spectrum will reflect this maximum probability in terms to the maximum
absorbance measured when doing UV/Vis spectroscopy.
Transition Profiles

Absorbance ?

2
1
=0

Absorption Spectrum

1
=0

3
4
5
6

=0

ro,i ro,f

Ch 14: Electronic Spectroscopy

Absorption Energy ?

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