Term Symbols

You may want to

review section 13.9 on
term symbols for
atoms.

g
16

Term Symbols

Component of orbital
angular about the
internuclear axis,
Multiplicity: 2S+1
Overall parity, u or g
Overall reflection
symmetry

17

Term Symbol
Component of orbital angular about the
internuclear axis,
is denoted by the symbols: , , ,
for values of 0, 1, 2,
Example:
The single electron in the ground state
of H2+ has a value of since orbitals
have zero orbital angular momentum.
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Term Symbol
Example:
A electron has one unit of angular momentum
about the internuclear axis.
If there is only one electron outside a closed
shell, then = .
If there are two electrons, then can be either
or .
if they are traveling opposite directions, in
which case they occupy different orbitals.
if they are traveling in the same direction, in
which case they occupy the same orbitals.
19

Term Symbol: Multiplicity

Multiplicity: 2S+1
S = sum of s values from each electron.
s is always .
The total spin angular momentum is
= 0, 1, 2, S (Note used here is not a term symbol)
For the ground state of O2, 12*2142 *2 where
there are two unpaired electrons in each the two
degenerate * orbital, the multiplicity
ultiplicity a triplet since
each s value is , making S =1, Making the
multiplicity = 2(1) +1=0.
The term symbol is 3.
20

Term Symbol: Multiplicity

The multiplicity for the single electron in
H2+ is 2, since S= and 2(
2()+1=2.
This makes the term symbol: 2

21

Term Symbol: Parity

As mentioned earlier:
A bonding orbital has even parity, g .
An antibonding orbital has odd parity, u.
A bonding orbital has odd parity, u .
An antibonding orbital has even parity, g.

22

Term Symbol: Overall Parity

If there are several electrons, the overall
parity is calculated by using
gg=g
uu=g
ug=u
These rules are generated by
interpreting g as +1 and u as 1.
23

Term Symbol: Parity

The term symbol for the single electron
in H2+ is therefore: 2g.
The term symbol for the ground state of
O2, with an electron configuration of:
12*2142*2 or g2u2u2 u2g1g1
is 3g.

24

Term Symbol: Overall Reflection Symmetry

A superscript
denotes the behavior
of the molecular
wavefunction under
reflection in a plane
containing the
nuclei.

25

Term Symbol: Overall Reflection Symmetry

If, for convenience, we think of O2 as having
one electron in 2x, which changes sign
under reflection in the yz-plane, and the other
electron in 2y, which does not change sign
under reflection in the same plane, the overall
reflection symmetry is
(closed shell) (+) () = ()
and the full term symbol of the ground
electronic state of O2 is 3g
26

Term Symbol: Overall Reflection Symmetry

27

Term Symbols and

the Excited State
The term symbols
of excited electronic
states are
constructed in a
similar way.

28

O2 in Ground and Excited States

29

Selection Rules
A number of selection rules govern which
transitions between allowed states of a
molecule will be observed in its electronic
spectrum.
The selection rules concerned with changes in
angular momentum are:
= 0, 1 S = 0 = 0 = 0, 1
where = + is the quantum number for
the total angular momentum (orbital and
spin) along the internuclear axis
30

= +

31

Selection Rules
These selection rules arise from the
conservation of angular momentum and
the fact that a photon has a spin of 1.

32

Selection Rules
Two of the selection rules are concerned
with changes in symmetry.
For terms, only and + +
are allowed.
The Laporte Selection Rule states
that the only allowed transitions are
transitions that are accompanied by a
change in parity.
33

Forbidden Transitions
Since only, g g and
u u transitions are allowed,
g g transitions are
forbidden.
forbidden.
However, if the molecule
eliminates its center of
symmetry through a vibration,
a vibronically allowed
transition may occur
(although it may be weak).
34

Practice
Be sure to practice SelfSelf-test 17.1
without looking at the answer.

35

Vibrational Structure
The FranckCondon principle states:
Because the nuclei are so much more
massive than the electrons, an electronic
transition takes place very much faster
than the nuclei can respond.

36

Vibrational Structure
As a result of the transition, electron density
is rapidly built up in new regions of the
molecule and removed from others, and the
initially stationary nuclei suddenly experience
a new force field.
They respond to the new force by beginning
to vibrate, and (in classical terms) swing
backwards and forwards from their original
separation, which was maintained during the
rapid electronic excitation.
37

Vibrational Structure
The stationary equilibrium
separation of the nuclei in
the initial electronic state
therefore becomes a
stationary turning point in
the final electronic state.

38

FranckCondon Principle and

Quantum Mechanics
The quantum mechanical
version of the FranckCondon
principle refines this picture.
Before the absorption, the
molecule is in the lowest
vibrational state of its lowest
electronic state; the most
probable location of the nuclei
is at their equilibrium
separation, Re.
39

FranckCondon Principle and

Quantum Mechanics
The electronic transition is
most likely to take place when
the nuclei have this separation.
When the transition occurs,
the molecule is excited to the
state represented by the upper
curve.

40

FranckCondon Principle and

Quantum Mechanics
According to the FranckCondon
principle, the nuclear framework
remains constant during this
excitation, so we may imagine
the transition as being up the
vertical line
The vertical line is the origin of
the expression vertical
transition, which is used to
denote an electronic transition
that occurs without change of
nuclear geometry.
41

Vibrational Structure
The vertical transition cuts through several
vibrational levels of the upper electronic
state. The level marked * is the one in which
the nuclei are most probably at the same
initial separation Re (because the vibrational
wavefunction has maximum amplitude there),
so this vibrational state is the most probable
state for the termination of the transition.
42

Vibrational Structure
However, it is not the only accessible
vibrational state because several nearby
states have an appreciable probability of
the nuclei being at the separation Re.
Therefore, transitions occur to all the
vibrational states in this region, but most
intensely to the state with a vibrational
wavefunction that peaks most strongly
near Re.
43

Transitions Between Energy

Levels and Nuclear Separation
The upper curve is usually
displaced to greater bond
lengths because
electronically excited
orbitals usually have more
antibonding character.

44

Electronic Spectra of Polyatomic Molecules

The absorption of a photon can often be
traced to the excitation of specifc types
of electrons or to electrons that belong
to a small group of atoms in a
polyatomic molecule, a R-C=O.

45

10

Chromophores
Groups with characteristic optical absorption
are called chromophores.
chromophores.

46

Absorption Characteristics Some

Groups and Molecules

47

d-d Transitions
All five d orbitals of a given shell are
degenerate in a free atom.
In a d-metal complex, where the immediate
environment of the atom is no longer
spherical, the
d orbitals are not all
degenerate, and electrons
can absorb energy by
making transitions between
them.
48

11

Ligand-Field Splitting

49

d-d Transitions
In an octahedral
complex, such as
[Ti(OH2)6]3+, the five
d orbitals of the
central atom are split
into two sets, a triply
degenerate set
labeled t2g and a
doubly degenerate
set labeled eg.
50

d-d Transitions

51

12

d-d Transitions
The three t2g orbitals lie below the two
eg orbitals; the difference in energy is
denoted O and called the ligand-field
splitting parameter (the O denoting
octahedral symmetry).
The d orbitals also divide into two sets in
a tetrahedral complex, but in this case
the e orbitals lie below the t2 orbitals
and their separation is written T.
52

d-d Transitions
Neither separation is large, so transitions
between the two sets of orbitals typically
occur in the visible region of the
spectrum.
The transitions are responsible for many
of the colors that are so characteristic of
d-metal complexes.
53

d-d Transitions
As an example, the
spectrum of [Ti(OH2)6]3+
near 20 000 cm-1 (500 nm)
is shown here, and can be
ascribed to the promotion
of its single d electron from
a t2g orbital to an eg orbital.
The wavenumber of the
absorption maximum
suggests that O = 20 000
cm-1.
54

13

d-d Transitions

55

d-d Transitions and the Laporte Rule

Since g g transitions
are forbidden by the
Laporte rule,
rule, we can
deduce that these
transitions from a t2g

orbital to an eg orbital
are vibronically allowed
transition because of
asymmetric vibrations.
56

Charge-Transfer Transitions
A complex may absorb radiation as a result of
the transfer of an electron from the ligands
into the d orbitals of the central atom, or vice
versa.
In such charge-transfer transitions the
electron moves through a considerable
distance, which means that the transition
dipole moment may be large and the
absorption is correspondingly intense.
57

14

Charge-Transfer Transitions
This mode of chromophore activity is
shown by the permanganate ion, MnO4,
and accounts for its intense violet color
(which arises from strong absorption
within the range 420700 nm).
In this oxoanion, the electron migrates
from an orbital that is largely confined to
the O atom ligands to an orbital that is
largely confined to the Mn atom.
58

SatinSatin-Ribbon Dyed Using a

Permanganate Compound

59

Charge-Transfer Transitions
It is therefore an example of a ligandto-metal charge-transfer transition
(LMCT).
The reverse migration, a metal-toligand charge-transfer transition
(MLCT), can also occur.

60

15

Charge-Transfer Transitions
An example is the transfer of a d
electron into the antibonding orbitals
of an aromatic ligand.
The resulting excited state may have a
very long lifetime if the electron is
extensively delocalized over several
aromatic rings, and such species can
participate in photochemically induced
redox reactions.
61

* Transitions
Absorption by a C=C double
bond excites a electron
into an antibonding *
orbital.
The chromophore is hence a
* transition.

62

* Transitions
Its energy is about 7 eV for an
unconjugated double bond, which
corresponds to an absorption at 180 nm
(in the ultraviolet).
When the double bond is part of a
conjugated chain, the energies of the
molecular orbitals lie closer together and
the * transition moves to longer
wavelength.
63

16

* Transitions
The transition may even lie in the visible
region if the conjugated system is long like in
the molecules in retina.

64

* n Transitions
Lone pairs of electrons on the oxygen atom in
carbonyl compounds (R(R-C=O) can also
undergo electronic transitions.
Although molecular orbital theory assumes
that electrons are spread throughout the
entire atom, lone pairs (from a Lewis
structure perspective) are electrons that are
essentially confined around an given atom
and do not involvr themselves in bonding.
65

* n Transitions
One of the lone pairs
electrons can be excited to
a * orbital of the carbonyl
group.
Typical absorption energies
are about 4 eV (290 nm).
Because * n transitions
in carbonyls are symmetryforbidden, the absorptions
are weak.
66

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