Chem 341

Coordination Chemistry – Electronic Spectra

Chapter 11: pp 409-418
HW: 1 2 3c 4c 5a 6 7 8 9 10

Goals: Use Beers Law to calculate Abs; convert wavelength

into wavenumbers; Derive ground state term symbols

Upcoming:
11/18, 11/21: Ch. 11. Electronic transitions in metal complexes
11/23 no class
11/28, 11/30: Acc. Chem. Res. 2003, 36, 876-887
Photochemistry for solar energy
12/2: Exam III

UMass Amherst  Created by Karsten Theis

Selection Rules for electronic transitions

 Laporte selection: transitions between states of

same parity are not allowed (g->u or u->g are
OK)
 Spin selection: transitions involving a change in
spin multiplicity are not allowed (4A2  4T1 ok;
4A  1T not OK)
2 1

 Charge transfers are often very intense

        ...    2
Which is the ground state for an octahedral d2 ion,
with weak-field ligands?

        ...    3

Which is the ground state for an octahedral d2 ion,

with weak-field ligands?
 t2g2 3T
1g (?)

 t2geg 3T
2g (?)

 t2g2 1T (?)
2g

 t2g2 1A
1g(?)

        ...    4
Which electronic transition is most intense?

 a) A  B
 b) A  C
 c) A  D

 3T  3T2g
1g

 3T  1T2g
1g

 3T  1A1g
1g

        ...    5

Which electronic transition is most intense?

 a) A  B

 3T  3T2g
1g

 But note the g g

parity! (not
intense)

        ...    6
Calculate Ground state Term Symbols
 Describe angular momentum (spin and orbital)
using LS coupling (Russell-Suanders)
 Write out electron config. Find L and S

 ML = ml MS = ms
 ML = 0, ±1, ±2…±L MS = 0, ±1, ±2…±S

 The ground state has maximal spin mulitpliticity!

 The ground state has highest S (Hunds rule)

 Tiebreaker; state with highest L

        ...    7

Easy way for ground state term symbols

 To find maximal spin multiplicity (2S+1) and highest
orbital angular momentum (L):
 Write ml values for the valence subshell(s)
 Eg: d4 ion

 s1p1 ion

        ...    8
All Terms: go through the microstates! Ex: 15
microstates for p2 ion (eg: C atom)

        ...    9

Reducing microstates to the Free Atom States

(AKA Terms)
 Break down microstates into
rectangular groups, to figure out L.
 (2S+1)L for spin multiplicity
 Ground state has maximum
multiplicity

        ...    10
Beers Law
 A = lc l (pathlength); c (mol/L);  (M-1 cm-1)
 A = log (Io/I)
 E = h = hc/= hcത

 h = 6.626 x 10-34 Js
 c = 2.998 x 108 m s-1
  (frequency, s-1)
 ത (wavenumber, cm-1)
        ...    11

        ...    12
450 550 650

        ...    13

        ...    14
        ...    15

        ...    16