Scribd
Upload
208 views3 pages

Electronic Selection Rules

This document discusses electronic selection rules for transitions in inorganic chemistry. It establishes that transitions are allowed if both the spin and orbital selection rules are satisfied. The spin selection rule requires the spin states to be the same, while the orbital selection rule requires the direct product of the initial and final orbital states to contain the totally symmetric representation. Ligand-to-metal and metal-to-ligand charge transfer transitions are also discussed and shown to have larger molar absorptivities than d-d transitions due to changes in orbital symmetry.

Uploaded by

Rojo John
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
208 views3 pages

Electronic Selection Rules

This document discusses electronic selection rules for transitions in inorganic chemistry. It establishes that transitions are allowed if both the spin and orbital selection rules are satisfied. The spin selection rule requires the spin states to be the same, while the orbital selection rule requires the direct product of the initial and final orbital states to contain the totally symmetric representation. Ligand-to-metal and metal-to-ligand charge transfer transitions are also discussed and shown to have larger molar absorptivities than d-d transitions due to changes in orbital symmetry.

Uploaded by

Rojo John
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 3

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


Page 1 of 3
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


Page 2 of 3
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


Page 3 of 3

You might also like