5.

04, Principles of Inorganic Chemistry II

MIT Department of Chemistry
Lecture 31: Electronic Selection Rules

Selection rules for electronic transitions determine whether a transition is

allowed or forbidden. The integrated intensity or oscillator strength, f, of an
absorption band is related to the transition moment integral, M,

molar absorptivity coefficient

2
f = 4.315104
dv =1.08510 11
 gs M es

 
where M = μ   e
r  i

M transforms as x, y, z
 i
electric dipole moment
electric polarization

The Born-Oppenheimer principle allows wavefunction to be separated into

electronic and vibronic components…  = esv
spin vibrational
electronic
Thus the transition moment integral becomes

M =
v
v
e μ̂
e 
s
s 

This integral must be non zero for the transition to be allowed. Ignoring the
vibronic component of the wave function, M will be non zero iff

e μ̂
e  and
s
s  are
0

For
s
s 
0… s = s’ thus the spin selection rule establishes that only

transitions between states of the same spin (S = 0) will be allowed.

The orbital or Laporte selection rule states that
e μ̂
e 
0 for an allowed

transition. This integral will be non-zero iff the direct product contains the
total symmetric representation (i.e. function must be even over all space)

 
 e 

(μˆ )
(e ) must contain a1(g)
 
transforms as x, y, z

5.04, Principles of Inorganic Chemistry II Lecture 31

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Ligand Field or dd transitions:

For d - orbitals… (qs) and ’(es) will be of g symmetry.

μ̂ transforms as u

Hence transition moment integral transforms as g x u x g = u… can’t be

totally symmetric. Hence d-orbitals are formally forbidden. This is why they
are weak:
 ~ 10-2 to 102 M-1cm-1

Charge Transfer transitions: two types, ligand-to-metal charge transfer

(LMCT) and metal-to-ligand charge transfer (MLCT).

LMCT transition promotes an electron from a ligand-based orbital (primarily

of p-character, and hence u symmetry) to an orbital that is primarily metal-
based (of g symmetry)…

Mn+L  M(n-1)+L

hence M transforms as g x u x u
g. These transitions are therefore much

stronger than d-d with  ~ 5000 – 50000 M-1cm-1.

Consider MO diagram of ML6 (Oh) complex with
-donating ligands:

ground state  a1g 

 M = ((es))
t1u
a1g = ((es))
t1u
μ̂  t iu 
will be non-zero if
totally symmetric…

L()  eg (M-L*): L(
)  eg (M-L*):

t1u ()  eg  allowed t1g(
)  eg
eg()  eg allowed  t2u(
)  eg can convince oneself
a1g()  eg allowed  t1u(
)  eg pretty quickly that
t2g(
)  eg ((es)) x t1u will
contain a1g iff ((es)) =
allowed transitions are ones t1u.
that contain t1u

5.04, Principles of Inorganic Chemistry II Lecture 31

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Consider the following data for LMCT transitions:

Complex E(LMCT) / cm-1 Complex E(LMCT) / cm-1

OsCl62 24 - 30,000 OsCl63 35,500
OsBr62- 17 – 25,000 -- -
OsI62- 12 – 18,000 OsI63- 19,100

As move from Cl-  I-, halide more easily oxidized (lower EN)… for LMCT,
transition will therefore shift to lower energy. Similarly OsIV is more easily
reduced than OsIII, hence OsX62- have lower energy LMCTs (as compared to
OsX63-)

MLCT transitions promote an electron from metal-based orbital to ligand
*

orbital. Again, p character introduced into transition. For same reasons as
LMCT, MLCTs possess  ~ 5000 – 50,000 M-1cm-1,

Mn+L  M(n+1)+L-

Allowed transitions for a ML6 (L =
acceptor) complex are:

t2g  t1u (
*)�

t2g  t2u (
*)�

5.04, Principles of Inorganic Chemistry II Lecture 31

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