TRANSISI ELEKTRONIK

Five Slides About: UV-Vis Spectroscopy

and Tanabe-Sugano Diagrams
Sabrina G. Sobel
Hofstra University
Sabrina.G.Sobel@hofstra.edu

Created by Sabrina.G.Sobel, Hofstra University (Sabrina.G.Sobel@hofstra.edu) and posted

on VIPEr (www.ionicviper.org) on March 8, 2014. Copyright Sabrina G. Sobel 2014. This
work is licensed under the Creative Commons Attribution-NonCommerical-ShareAlike 3.0
Unported License. To view a copy of this license visit
http://creativecommons.org/about/license/
 d-Orbital Splitting in Transition Metal
Complexes
Octahedral (Oh) symmetry:
eg
d-orbitals split into t2g and eg sets
Do Do is the splitting energy, and is
t2g
dictated by ligand field strength
(see spectrochemical series)
Tetrahedral (Td) symmetry:
t2 d-orbitals split into e and t2 sets
e
DT is always smaller than Do since
total ligand field strength is less
Spectrochemical Series
CN-, CO > NO2-, phen > bpy > SO32- > NH3 > NCS- > H2O > OH- > F- > Cl- > SCN- > Br- > I-
 UV-Vis Spectroscopy of Transition
Metal Complexes
Symmetry Rules:
LaPorte: allowed transitions occur between orbitals of
opposite symmetry WRT inversion (gerade (even) and
ungerade (odd) in character tables)
Spin Multiplicity: allowed transition occur when spin
multiplicity is unchanged
d0 metal cations: charge-transfer transitions
LaPorte allowed; ligand p* to metal d orbital
d1 to d9 metal cations: dd transitions
LaPorte forbidden; same orbital type
d10 metal cations: no dd transitions because
the orbitals are filled
 d d Transitions
and Color
TM complex (d1 to d9)
absorbs visible light
Transmitted light is opposite
color to absorbed light
Energy of absorbed light is
proportional to D
Strong field ligand: low nm
Weak field ligand: high nm
Example: Fe(phen)32+
lmax = 508 nm (green)
Transmitted color: red-
orange
 d d Transitions and Color

Cobalt complexes with: (a) CN, (b) NO2, (c) phen, (d) EN, (e) NH3,
(f) gly, (g) H2O, (h) oxalate2, (i) CO32.

Complexes are arranged in order of decreasing Doct

Color transmitted increases in energy from yellow olive
 Russell-Saunders Coupling
Review: Example: Cr(II); d4
http://wwwchem.uwimona.edu 1. Orbital diagram
.jm/courses/RScoupling.html
Determining ground state of
Transition Metal cations
1. Draw d-orbitals and fill with L : -2 -1 0 +1 +2
# electrons for desired ion
2. Calculate Spin Multiplicity = 2. 4+1 = 5
#unpaired electrons +1 = S 3. 2+1+0+(-1) = 2 D
3. Find maximum ML (ml = -2, 4. 5D is the ground state term
-1, 0, 1, 2 for d orbitals) = L Spin-allowed transitions will
4. Ground state term: be pentet to pentet
SL = (step 2)(Step 3)
 Oh Tanabe-Sugano Diagrams
Symmetry lowering from
spherical to octahedral
electrical field is applied to
ground state and excited
state terms
Relative energies of states
are plotted against ligand
field strength
Term Degeneracy States in an octahedral field
S 1 A1g
P 3 T1g d4 ion g.s.
D 5 Eg + T2g
F 7 A2g + T1g + T2g
G 9 A1g + Eg + T1g + T2g
H 11 Eg + T1g + T1g + T2g
I 13 A1g + A2g + Eg + T1g + T2g + T2g
Oh T-S Diagram for a d4 ion
 Oh Tanabe-Sugano Diagrams
Oh T-S Diagram for a d4 ion
B = Racah Parameter; takes
into account electron
repulsion energy
X-axis: D/B
Y-axis: E/B
High spin vs. low spin
eg

t2g
5D 3G

Spin allowed transitions:

5E to 5T2 (UV-Vis range)
3T1 to 3E (large energy gap!)
[Cr(CH3CO2)2(H2O)]2 is brick red; CrCl2(H2O)4 is green
 Warna dari senyawa kompleks
berasal dari absorpsi dari
spektrum visibel dengan
transmisi dari frekuensi sinar
yang terserap
Ti(H2O)63+ tampak berwarna
ungu (merah + Biru) karena
menyerap warna hijau pada
~500nm = ~20.000 cm-1
Adsorpsi pada beberapa
panjang gelombang tersebut
mengikuti hukum Lambert-
Beer
 Transisi Elektronik
Dalam model teori medan kristal (CFT), absorpsi karena
elektron dari orbital d terendah naik ke orbital d lebih
tinggi

Perubahan konfigurasi menyebabkan perubahan dalam

sistem term-nya
Untuk ion d1 bebas, term pada keadaan dasar adalah
2D, memiliki lima kali degenerasi muncul dari lima
kemungkinan elektron menempati dalam lima orbital d
degenerasi.
 Transisi Elektronik
Dalam medan oktahedral term-nya adalah split
kedalam term keadaan dasar baru yang cocok
dengan konfigurasi t2g1 eg0 dan term keadaan
tereksitasi yang cocok adalah konfigurasi t2g0 eg1.

Keadaan dasar baru bisa dilambangkan 2T2g, dan

untuk keadaan tereksitasi dilambangkan 2Eg.
 Transisi Elektronik
Perbedaan energi antara dua keadaan adalah
0 =10Dq, yang mana secara energenetikal
ekuivalen dengan frekuensi absorbansi

Notasi keadaan untuk absorbansi transisi

adalah
 Term Ion Ion Bebas untuk untuk
Konfigurasi d1-10
Transisi ion logam dengan konfigurasi d2-d8
memiliki lebih dari satu term

Term untuk dn adalah sama dengan d10-n

Penentuan Keadaan dasar dari Term
Ion Bebas

Tuliskan Konfigurasi
sesuai aturan Hund
Tentukan term untuk L
=|ML|, dimana

Tentukan multiplisitas =
2S+1, dimana S =|Ms|
 Splitting dari Term Ion Bebas dalam
Berbagai Medan

Diagram Splitting untuk konfigurasi d1-

d9 dapat dibangun.
Splitting Term pada ion bebas
tergantung pada komplek simetri
Splitting term pada medan yang simetri
lain dapat disimpulkan sebagai
penurunan simetri dari Oktahedral,
atau dengan membangun term ion
bebas secara menurun yang
menghasilkan point group .
 Outline
Absorption spectroscopy
Types of transitions
atomic
molecular
d-d transitions
Transition moment
Microstates
Correlation diagrams
Tanabe-Sugano diagrams
Selection rules
 Interaction of Light with Matter

Rainbows Moon Light Two-slit exp Sand in Water

Glasses Butterfly Wings Holograms Sunsets
Mirage Sea Shells Shadow Blur
Refractometer Soap Bubbles

19
 Absorption Spectrosocpy

hn hn

Sample

We dont measure absorbance. We measure transmittance.

Sample Transmittance:
T = P/P0
P0 P
Absorbance:
(power in) (power out)
A = -log T = log P0/P
 Beers Law
The Beer-Lambert Law (l specific):

A=ecl Sample

A = absorbance (unitless, A = log10 P0/P)

P0 P
e = molar absorptivity (L mol-1 cm-1)
l = path length of the sample (cm) (power in) (power out)

c = concentration (mol/L or M)
l in cm

Concentration Absorbance
Path length Absorbance
Molar Abs. Absorbance
 Beers Law
The Beer-Lambert Law (l specific):

A=ecl Sample

A = absorbance (unitless, A = log10 P0/P)

P0 P
e = molar absorptivity (L mol-1 cm-1)
l = path length of the sample (cm) (power in) (power out)

c = concentration (mol/L or M)
l in cm

What are we actually

measuring/observing?
e

100 200 300 400 500

Wavelength (nm)
 Electronic Transitions
Interaction between an electromagnetic wave and the wave function of a
molecule/atom/material.
Transition between quantized energy states of an atom/molecule/material.
Exciting an electron from one quantum state to another.

hn
hn

Ground First Excited

State (S0) State (S1)
 Electronic Transitions
Spectral Features:
Number of transitions.
Energy of the transitions.
Intensity of the transitions.
e

100 200 300 400 500

Wavelength (nm)
 Electronic Transitions
Spectral Features:
Number of transitions. hn
Energy of the transitions.
Intensity of the transitions.

hn
e

100 200 300 400 500 hn

Wavelength (nm)
 Electronic Transitions
Spectral Features:
Number of transitions.
Energy of the transitions.
Intensity of the transitions.
Shape of the transition.

hn
e

100 200 300 400 500

Wavelength (nm) DE Transition Probability
 hn
Atomic Transition

Energy

hn

Ground State Excited State 27

 Hydrogen Absorption
H H

H H
H
H
H

white light source Hydrogen Sample Prism

Line
Spectrum

Rydberg Formula

1 1
E RH 2 2
nl nh

28
 Increasing Complexity

1 e-

10 e-

80 e-

Atomic Transitions
(movement of electrons)
250 e- +
Molecular Transitions
(movement of electron density)

29
 Types of Molecular Transitions

- *
lmax < 150 nm

p - p*
lmax 200 - 800 nm Absorption

s - s* p - p*
n - p* n - p*
lmax 150 - 300 nm
100 200 300 400 500
Wavelength (nm) 30
 Types of Molecular Transitions
Focus on Metal
[Co(H2O)6]2+ Centered
Transitions
Metal Centered (MC)
lmax 200 800 nm

MnO4-

MLCT LMCT MMCT

lmax 300 1000 nm lmax 300 1000 nm lmax 300 800 nm

31
 Colors of Metal Ions

Alexandrite

Cr3+ doped
BeAl2O4
 Colors of Metal Ions
Cr3+ doped
BeAl2O4 Uniform White Light

~400 nm = 4A2g to 4T1g

~600 nm = 4A2g to 4T2g

Sunlight

Candle Light

http://www.chemistry-blog.com/2013/08/22/alexandrite-effect-not-all-white-light-is-created-equal/
 Colors of Metal Ions
Ruby
~1% Cr3+ doped Al2O3
Absorbs yellow-green region
Emits red

Most expensive ruby (1.6 cm3) = $6.7 million

Al2O3 (1.5 cm3) = ~$500
Absorption Spectra of Metal Ions

Intensity

Energy
 Electronic Transitions
A=ecl
A = absorbance (unitless, A = log10 P0/P)
e

e = molar absorptivity (L mol-1 cm-1)

l = path length of the sample (cm)
100 200 300 400 500
c = concentration (mol/L or M)
Wavelength (nm)

Transition probability the probability of a particular transition

taking place.

Depends on:
1) Energy of the transition/incident light.
2) Orientation of the molecule/material.
3) Symmetry of the initial and final states.
4) Angular momentum (spin).
 States vs. Orbitals

S2
S1
Second Excited
Energy State (S2)

First Excited
S0
State (S1)

Single Orbital

Sum of Orbitals Ground

and electron State (S0)
occupations 37
 Transition Moment
The transition probability of one molecule from
S2 one state (Y1) to another state (Y1) is given by
S1 |M21|, the transition dipole moment, or
Y2 transition moment, from Y1 to Y2.

Energy Transition moment:

S0 Y1 where m is the electric dipole moment operator:

where Qn is charge, x n is the position vector

operator.

For an electronic transition to be allowed, the transition moment

integral must be nonzero.
 Transition Moment

e
e

100 200 300 400 500

Wavelength (nm)

Y1 Y2
hn

hn
 Transition Moment

e
e

100 200 300 400 500

Wavelength (nm)

If M21 = 0, then the transition probability is 0 and the transition from

Y1 to Y2 is forbidden or electric-dipole forbidden.
M21 = 0, e = 0
If M21 0, then the transition probability is not 0 and the transition
from Y1 to Y2 is not forbidden.
M21 0, e 0
Does not tell you definitively that it is
allowed or how intense it will be. Only
that it is not electric-dipole forbidden.
 Transition Moment
Y1
Y2

allowedness of a
transition
=

Irr. Rep. for the Irr. Rep. for the Irr. Rep. for the
hn linear basis
excited state ground state
(x, y, and z)

If the direct product DOES NOT contain the totally symmetric representation
(A, A1, A1g), then the transition is FORBIDDEN by symmetry arguments.

If the direct product DOES contain the totally symmetric representation (A,
A1, A1g), then the transition is ALLOWED by symmetry arguments.

The integral will be exactly zero if the Irr. Rep. of the direct
product does not contain A, A1, Ag , A1g or A.
 Direct Product
Direct product: The representation of the product of two
representations is given by the product of the characters of the
two representations.

42
Direct Product Table

43
 Example (dz2 to pz)
allowedness of a
transition
=

Irr. Rep. for the Irr. Rep. for the

excited state Irr. Rep. for the ground state
linear basis
(x, y, and z)

(z) (x) (y)

p (pz)
D2h B1u B3u B2u B1u B1u

hn
s
Ag

(z2) (xy) (xz) (yz) (x2-y2)

d (dz2)
Ag B1g B2g B3g Ag Ag Ag
 Example (dz2 to pz)
Irr. Rep. for the Irr. Rep. for the Irr. Rep. for the
excited state linear basis ground state
(x, y, and z)

allowedness of
(pz)
= a transition

B1u B1u
x basis B1u B3u Ag = B2g
hn
y basis B1u B2u Ag = B3g
(dz2)
Ag Ag
z basis B1u B1u Ag = Ag
D2h
 Example (dz2 to pz)
(pz) x basis B1u B3u Ag = B2g
B1u B1u

hn
y basis B1u B2u Ag = B3g

(dz2) z basis B1u B1u Ag = Ag

Ag Ag

The transition is forbidden if the direct product does not contain A, A1, Ag , A1g or A.
The transition is allowed if the direct product does contains A, A1, Ag , A1g or A.

z polarized =
allowed
hn x polarized =
forbidden
hn

y polarized =
dz2 pz forbidden
Allowed
 Example (dxy to pz)
allowedness of a
transition
=

Irr. Rep. for the Irr. Rep. for the

excited state Irr. Rep. for the ground state
linear basis
(x, y, and z)

(z) (x) (y)

p (pz)
D2h B1u B3u B2u B1u B1u

hn
s
Ag

(z2) (xy) (xz) (yz) (x2-y2)

d (dxy)
Ag B1g B2g B3g Ag B1g B1g
 Example (dxy to pz)
Irr. Rep. for the Irr. Rep. for the Irr. Rep. for the
excited state linear basis ground state
(x, y, and z)

allowedness of
(pz)
= a transition

B1u B1u
x basis B1u B3u B1g = B3g
hn
y basis B1u B2u B1g = B2g
(dxy)
B1g B1g
z basis B1u B1u B1g = B1g
D2h
 Example (dxy to pz)
(pz) x basis B1u B3u B1g = B3g
B1u B1u

hn
y basis B1u B2u B1g = B2g

(dxy) z basis B1u B1u B1g = B1g

B1g B1g

The transition is forbidden if the direct product does not contain A, A1, Ag , A1g or A.
The transition is allowed if the direct product does contains A, A1, Ag , A1g or A.

z polarized =
forbidden
hn x polarized =
forbidden
hn

y polarized =
dxy pz forbidden
Forbidden
 Example (dx2-y2 or dxy,yz to px,y)
allowedness of a
transition
=

Irr. Rep. for the Irr. Rep. for the

excited state Irr. Rep. for the ground state
linear basis
(x, y, and z)
dx2-y2 to px,y
(px,y)
(z) (x) (y) E E
hn
C4v p
A1 E
(dx2-y2)
B1 B1

s dx2-y2 to px,y
A1
(px,y)
E E
(z2) (xy) (xz) (yz) (x2-y2) hn
d
A1 B 2 E B1 (dxz,yz)
E E
 Example (dx2-y2 or dxy,yz to px,y)
dx2-y2 to px,y
(px,y)
E E
hn Forbidden (z)
A1
(dx2-y2)
E B1 = E
B1 B1 E A1 + A 2 + B 1 + B2
Allowed (x,y)
dx2-y2 to px,y
Allowed (z)
(px,y) A1
E E E E = A 1 + A 2 + B 1 + B2
hn E E
Forbidden (x,y)
(dxz,yz)
E E
A 1 + A 2 + B 1 + B2

C4v
One Electron Octahedral

T2g Eg

Eg T1u T2g =
 One Electron Octahedral

Eg T1u T2g

Eg A2u + Eu + T1u + T2u

Forbidden (x, y, z) Eu + A1u + A2u + Eu + T1u + T2u + T1u + T2u

Six Electron Octahedral (Low spin)
Ground State Excited State

A1g T2g Eg

T1g + T2g
Six Electron Octahedral (Low spin)
Ground State Excited State

A1g T2g Eg

T1g + T2g

T1g
T1u A1g =
T2g
Six Electron Octahedral (Low spin)
Ground State Excited State

A1g T2g Eg

T1g + T2g

T1g
T1u A1g =
T2g

A1u + Eu + T1u + T2u

Forbidden (x, y, z)
A2u + Eu + T1u + T2u
Simple Cases
1 electron (two states)

Eg T1u T2g

5 electron (two states)

T1g
T1u A1g
T2g
More Complex Case (Oh d3)

Excited States

Eg
Ground State
T2g
More Complex Case (Oh d2, d3, d2, d8)
Ground State Excited States

eg
d2
t2g

eg
d3
t2g

eg
7
d
t2g

eg
8
d
t2g

There has to be an easier way to

describe transitions between states!
 Tanabe-Sugano Diagrams

d3
Useful for:
Electronic States
Relative Energies
Ligand Field Affects
Optical Transitions
Spin Multiplicities
High-Spin to Low-Spin Transitions
Estimate Do
 Getting to Tanabe-Sugano Diagrams

Electronic States
Term symbols
Microstate tables
Correlation diagrams
Tanabe-Sugano diagrams
Selection rules
 Quantum Numbers
PRINCIPAL (n): energy level, the distance the orbital is from the
nucleus
n = 1, 2, 3, 4

ANGULAR MOMENTUM: l, shape of the orbital

s = 0, p = 1, d = 2, f = 3

MAGNETIC: ml , spatial orientation

ml = 0 for s; -1, 0, +1 for p; -2, -1, 0, +1, +2 for d, etc.

SPIN: ms spin
ms = +1/2 or -1/2)
 Quantum Numbers

F atom
1s 2s 2p

The third electron is in the 2s orbital.

n= 2 l= 0 ml = 0 ms= +1/2

The eighth electron is in a 2p orbital.

n= 2 l= 1 ml = -1 ms= -1/2

Only describes single electron states!

What about multielectron states?

 Many Electron States
Many electron interactions are described by
Russel-Saunders or L-S coupling scheme

ML = total orbital angular momentum =ml

MS = total spin angular momentum = ms

Summarized by term symbols that contain:

- spin multiplicity (2S+1)
- angular momentum quantum number (L)
- the total angular momentum (J )

2S+1L
J

The interactions produce atomic states called microstates.

 Term Symbols
S represents the total spin angular momentum
S = total spin angular momentum = ms

+1/2 S = 1/2 2L
2S+1L J
J
+1/2 +1/2 -1/2 +1/2 S=1 3L
J

L specifies the total orbital angular momentum

L = angular momentum = ml

L=3 3F
J
For D orbitals ml = +2 +1 0 -1 -2
L=2 3S
L=0 J
ml = +2 +1 0 -1 -2

J = Total angular momentum L= 0 1 2 3 4

J = L+S, L+S-1, L+S-2,.L-S|
Term Symbol S P D F G
Spin Orbit Coupling
 Term Symbols
L = M L( m ax) M L = m l S = s

l = 2, ml = 2 1 0 -1 -2 Te rm
L S 2 S + 1 s ym bo l

2 1/2 2 2
D

3 1 3 3
F

3 3/2 4 4
F

2 5
2 5 D

6
0 5/2 6 S
 Term Symbols

We are only assigning one state at a time!

To assign all the states we turn to a microstate table!
 Microstate Table
A microstate table contains all possible combinations of ml and ms.
Each microstate represents a possible electron configuration.
It includes both ground and excited states.
Must obey the Pauli Exclusion Principle.

p2 total spin angular momentum

ML +1 0 -1
+2: 1+1-
1+0-
+1: 1+0+ 1-0-
1-0+
total orbital
angular momentum -1+1-
0: -1+1+ 0+0- -1-1-
-1-1+
-1+0-
-1: -1+0+ -1-0-
-1-0+
-2: -1+-1-
 Microstates
ML +1 0 -1
+2: 1+1-
1+0-
+1: 1+0+ 1-0-
1-0+
-1+1-
0: -1+1+ 0+0- -1-1-
-1-1+
-1+0-
-1: -1+0+ -1-0-
-1-0+
-2: -1+-1-
 Microstate Table Notation
p2 electron configuration
Two electrons in px, py and pz orbitals.
e- spin

ml = +1 0 -1 microstate:
Ground State ___ ___ ___ (1+,0+)
Configurations: ___ ___ ___ (0+,-1+) e- ml
___ ___ ___ (1+,-1+)

ml = +1 0 -1 microstate:
A few Excited State ___ ___ ___ (1+,1-)
Configurations: ___ ___ ___ (0+,0-)
___ ___ ___ (-1+,-1-)
 Microstate Table Notation

(1+,1-) (-1+,-1-) (1+,-1+) (1-,0-) (0-,-1-) (1+,-1-) (1-,0+) (0-,-1+)

(0+,0-) (1+,0+) (0+,-1+) (1-,-1-) (1+,0-) (0+,-1-) (1-,-1+)

15 total possible states

 Microstate Table
15 total possible states
(1+,1-) (-1+,-1-) (1+,-1+) (1-,0-) (0-,-1-) (1+,-1-) (1-,0+) (0-,-1+)
(0+,0-) (1+,0+) (0+,-1+) (1-,-1-) (1+,0-) (0+,-1-) (1-,-1+)

total spin angular momentum

total orbital
angular momentum
 Microstate Table
15 total possible states

X X X X

X X X X X

X X X X

Group Energetically equivalent states.

 Microstate Table
15 total possible states

X X X X

X X X X X

X X X X

Group Energetically equivalent states.

 Microstate Table
15 total possible states

X X X X

X X X X X

X X X X

Group Energetically equivalent states.

 Microstate Table
15 total possible states

X X X X

X X X X X

X X X X

Group Energetically equivalent states.

 Term Symbol from Microstate Tables

2S+1L
S = highest Ms
L = highest Ml

1D 3P 1S
5 equivalent states 9 equivalent states 1 state
 Relative Energies
1D 3P 1S
5 E equivalent states 9 E equivalent states 1 state

1. For a given electron configuration, the term with the greatest

multiplicity lies lowest in energy. (Hunds rule.)

2. For a term of a given multiplicity, the greater the value of L, the

lower the energy.

Lowest E Highest E
3P < 1D < 1S

Note: The rules for predicting the ground state always work, but they
may fail in predicting the order of energies for excited states.
 Microstate Table Notation
d2 electron configuration
Two electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.

ml = +2 +1 0 -1 -2 microstate
___ ___ ___ ___ ___ (2+, 1+)
___ ___ ___ ___ ___ (1+, 0+)
Configurations: ___ ___ ___ ___ ___ (2+, 2-)
___ ___ ___ ___ ___ (1+, -2-)
___ ___ ___ ___ ___ (2+, -1+)

etc.

45 microstates (ML = 4-4, and MS=1, 0 or -1)

 Microstate Table Notation
d2 electron configuration
Two electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.
 Microstate Table Notation
d2 electron configuration
Two electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.

X
X X X X
X X X X X
XX X X X X XX
XX X X X X X XX
XX X X X X XX
X X X X X
X X X X
X
 Microstate Table Notation
d2 electron configuration
Two electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.

X
X X X X
X X X X X
XX X X X X XX
XX X X X X X XX
XX X X X X XX
X X X X X
X X X X
X

2S+1L
S = highest Ms
L = highest Ml 1G
L= 0 1 2 3 4
Term Symbol S P D F G
 Microstate Table Notation
d2 electron configuration
Two electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.

X
X X X X
X X X X X
XX X X X X XX
XX X X X X X XX
XX X X X X XX
X X X X X
X X X X
X

2S+1L
S = highest Ms
L = highest Ml 1G 3F
L= 0 1 2 3 4
Term Symbol S P D F G
 Microstate Table Notation
d2 electron configuration
Two electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.

X
X X X X
X X X X X
XX X X X X XX
XX X X X X X XX
XX X X X X XX
X X X X X
X X X X
X

2S+1L
S = highest Ms
L = highest Ml 1G 3F 1D
L= 0 1 2 3 4
Term Symbol S P D F G
 Microstate Table Notation
d2 electron configuration
Two electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.

X
X X X X
X X X X X
XX X X X X XX
XX X X X X X XX
XX X X X X XX
X X X X X
X X X X
X

2S+1L
S = highest Ms
L = highest Ml 1G 3F 1D 3P
L= 0 1 2 3 4
Term Symbol S P D F G
 Microstate Table Notation
d2 electron configuration
Two electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.

X
X X X X
X X X X X
XX X X X X XX
XX X X X X X XX
XX X X X X XX
X X X X X
X X X X
X

2S+1L
S = highest Ms
L = highest Ml 1G 3F 1D 3P 1S
L= 0 1 2 3 4
Term Symbol S P D F G
 Microstate Table Notation
d2 electron configuration
Two electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.

1G 3F 1D 3P 1S

1. For a given electron configuration, the term with the greatest

multiplicity lies lowest in energy. (Hunds rule.)
2. For a term of a given multiplicity, the greater the value of L,
the lower the energy.
Lowest E Highest E
3F < 3P < 1G < 1D < 1S
Note: The rules for predicting the ground state always work, but they
may fail in predicting the order of energies for excited states.

Lowest E Highest E
Real Order 3F < 1D < 3P < 1G < 1S
 Microstate Table
d3 electron configuration
Three electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.

ml = +2 +1 0 -1 -2 microstate
___ ___ ___ ___ ___ (2+,2-,1+)
 Microstate Table Notation
d1 electron configuration
Two electrons in dxy, dxz, dxy, dz2 and dx2-y2 orbitals.

ml = +2 +1 0 -1 -2 microstate (2+)
___ ___ ___ ___ ___ (2+) (1+)
___ ___ ___ ___ ___ (1+)
Configurations: ___ ___ ___ ___ ___ (0+) (0+)
___ ___ ___ ___ ___ (-1+)
___ ___ ___ ___ ___ (-2+)
(0+)

(0+)
2S+1L
2D
S = highest Ms
L = highest Ml
 Ligand Field Dependence
One d electron (d1)
dxy, dxz, dxy, dz2 and dx2-y2 ___ ___ ___ ___
___ ___ ___ ___ ___ ___

___ ___ ___ ___ ___

___ ___ ___ ___ ___
___ ___ ___ ___ ___ 2D
___ ___ ___ ___ ___ eg ___ ___
___ ___ ___ ___ ___ t2g ___ ___ ___
___ ___ ___ ___
___ ___ ___ ___ ___ ___

Degenerate Infinite
symmetric field Real molecules Oh field
Absence of ligand field. Correlation Diagram Strong ligand field.
Free-ion term. Orgel Diagram Coord Complex.
All d orbitals are E equal. d orbitals not degenerate
dz2 and dx2-y2 higher E
dxy, dxz and dyz lower E
 Correlation Diagram
d1 Term symbols d2 Term symbols
= 2D = 3F, 1D, 3P, 1G, 1S
 Correlation Diagram ___ ___
___ ___ ___

___ ___
Term # of States Terms in Oh Field
S 1 A1g ___ ___ ___
P 3 T1g
D 5 T2g + Eg
F 7 T1g + T2g + A2g
G 9 A1g + Eg+T1g+T2g
___ ___
___ ___ ___

___ ___
___ ___ ___

___ ___
___ ___ ___

___ ___
___ ___ ___
 Correlation vs. Tanabe-Sugano Diagrams
Correlation Diagram Tanabe-Sugano Diagram
d2

Number of states. Number of states.

General sense of field effects. Field effects.
Only qualitative. Quantitative.
 Tanabe-Sugano Diagrams
d2
Relative energies.
Ligand field affects.
Electronic states with the same
symmetry can not cross (non-
crossing rule).
Energy

Curvature (1E and 1E).

Ground state on the x-axis.
Transitions between states.

Ligand Field
 Tanabe-Sugano Diagrams
d2

Excited 10 possible transitions

States
Not all transition
Energy

probabilities are equal!

Ground
State

Ligand Field
 Selection Rules
Selection rules determine the probability (intensity) of the transition.

Symmetry (Laporte) Selection Rule: The initial and final

wavefunctions must change in parity. Parity is related to the
orbital angular momentum summation over all elections li, which
can be even or odd; only even odd transitions are allowed.
Transitions between the orbitals of the same sub shell are
forbidden.

Spin Selection Rule: There must be no change in the spin

multiplicity (DS = 0) during the transition.
i.e. the spin of the electron must not change during the transition.
 Selection Rules
Selection rules determine the probability (intensity) of the transition.
Symmetry (Laporte) Selection Rule: The initial and final wavefunctions must
change in parity. Only even (g) odd (u) transitions are allowed. Transitions
between the orbitals of the same sub shell are forbidden.
gg uu gu ug
Forbidden Allowed

For Oh complexes
allowedness of a
= = T1u
transition

Forbidden u = g u g Direct Product Rules

Forbidden u = u u u g u =u
g = g u u g g =g
Allowed
u u u =g
Allowed g = u g
 Selection Rules
Selection rules determine the probability (intensity) of the transition.
Symmetry (Laporte) Selection Rule: The initial and final wavefunctions must
change in parity. Only even (g) odd (u) transitions are allowed. Transitions
between the orbitals of the same sub shell are forbidden.
gg uu gu ug
Forbidden Allowed
For Oh complexes
dd
Forbidden
t2g eg
dp
Allowed
t2g t1u
pp
Forbidden
t1u t1u
 Selection Rules
Selection rules determine the probability (intensity) of the transition.

Symmetry (Laporte) Selection Rule: The initial and final

wavefunctions must change in parity. Parity is related to the
orbital angular momentum summation over all elections li, which
can be even or odd; only even odd transitions are allowed.
Transitions between the orbitals of the same sub shell are
forbidden.

Spin Selection Rule: There must be no change in the spin

multiplicity (DS = 0) during the transition.
i.e. the spin of the electron must not change during the transition.
 Selection Rules
Selection rules determine the probability (intensity) of the transition.
Spin Selection Rule: There must be no change in the spin multiplicity (DS = 0) during
the transition. i.e. the spin of the electron must not change during the transition.

hn hn

1L 1L* 1L 3L*
Allowed Forbidden

1T 1T2
1 Allowed

1T 3T Conservation of
1 1 Forbidden
angular momentum.
3T 1A2
1 Forbidden
 Tanabe-Sugano Diagrams
Complete Diagram Spin Only Diagram
d2
 Selection Rules
Selection rules determine the probability (intensity) of the transition.

Symmetry (Laporte) Selection Rule: The initial and final

wavefunctions must change in parity.

Spin Selection Rule: The spin of the electron must not change
during the transition.

Transition max (M1cm1)

Spin and Symmetry forbidden "d-d" bands 0.02 - 1

Spin allowed and Symmetry forbidden "d-d" bands 1 - 10

Spin and Symmetry allowed CT bands 103 - 5 x 104

 Tanabe-Sugano Diagrams
All d-d transitions are
d2 symmetry (Laporte)
forbidden

Spin-allowed transitions
3T 3T
1g 2g
3T 3T1g
1g
Energy

3T 3A2g
1g

Ligand Field
 d1 and d9 Tanabe-Sugano Diagram
d1 d9

[Ti(H2O)6]3+
 d3 Tanabe-Sugano Diagram
d3

Ruby
~1% Cr3+ doped Al2O3
 d3 Tanabe-Sugano Diagram

d8
 d6 Tanabe-Sugano Diagram
d6
High Low
Spin Spin
Energy

High Low
Spin Spin
5T 1A
2g 1g

Ligand Field

Smaller Do The Spectrochemical Series Larger Do

I- < Br- < Cl- < OH- < RCO2- < F- < H2O < NCS- < NH3 < en < NO2- < phen < CO, CN- 107
 Tanabe-Sugano Diagram

d4 d5 d7
 d6 Tanabe-Sugano Diagram

Complex Ion labs (nm)

[Co(H2O)6] 3+ 600, 400
[Co(NH3)6] 3+ 475, 340
[Co(en)3] 3+ 470, 340

Smaller Do The Spectrochemical Series Larger Do

I- < Br- < Cl- < OH- < RCO2- < F- < H2O < NCS- < NH3 < en < NO2- < phen < CO, CN-
 Selection Rules
Selection rules determine the probability (intensity) of the transition.

Symmetry (Laporte) Selection Rule: The initial and final

wavefunctions must change in parity.

Spin Selection Rule: The spin of the electron must not change
during the transition.

Transition max (M1cm1)

Spin and Symmetry forbidden "d-d" bands 0.02 - 1

Spin allowed and Symmetry forbidden "d-d" bands 1 - 10

Spin and Symmetry allowed CT bands 103 - 5 x 104

Why do we see forbidden transitions at all?

 Allowing Forbidden Transitions
Mechanisms that make forbidden electronic transitions to be
allowed

1) Vibronic Coupling: Electronic states coupled to vibrational

states help overcome the Laporte selection rule.

2) Spin-orbit Coupling: Spin and orbital angular momenta can

interact to make spin forbidden transitions allowed.j

3) Mixing of states: -acceptor and -donor ligands can mix with

the d-orbitals transitions are no longer purely d-d.
 Vibronic Coupling
Ground State Excited State

Oh symmetry
A1g T1g + T2g

The transition probability of one molecule from

one state (Y1) to another state (Y1) is given by
|M21|, the transition dipole moment, or T1g
transition moment, from Y1 to Y2. T1u A1g =
T2g

A1u + Eu + T1u + T2u

A2u + Eu + T1u + T2u
allowedness of a
transition
= Electronically Forbidden (x, y, z)
 Vibronic Coupling
Ground State Excited State

Oh symmetry
A1g T1g + T2g

For octahedral complex, there are 15 vibrational normal modes with

irreducible representations:

Vibrational transition couple with electronic transition:

 Vibronic Coupling

excited state ground state

vibrational wavefunction vibrational wavefunction
 Vibronic Coupling
For Oh

Gev Ggv
T1g
(A1g, Eg , T1u , T2g , T2u) T1u A1g A1g
T2g

T1uand T2u vibrations can couple with the electronic

transition to form allowed transitions.
 Vibronic Coupling

excited state ground state

vibrational wavefunction vibrational wavefunction

T1uand T2u vibrations can couple

with the electronic transition to
form the allowed vibronic
transition.
Spin-Orbit Coupling

Lower
Energy

117
Nicholas J. Turro, Principles of Molecular Photochemistry
 Spin-Orbit Coupling
Spin Selection Rule: There must be no change in the spin multiplicity (DS = 0) during
the transition. i.e. the spin of the electron must not change during the transition.

hn hn

1L* 1L 3L*
Allowed Forbidden

Spin-orbit Coupling

Conservation of
angular momentum.
Spin-Orbit Coupling

Heavy Atoms
Pt, Ir, Os, I...

Ru(bpy)3
Os(bpy)3

119
Nicholas J. Turro, Principles of Molecular Photochemistry
 Mixing of States
d2
Tunabe-Sugano
diagram assumes
pure d-d transitions
Energy

Mixing of states: -acceptor and

-donor ligands can mix with the
d-orbitals transitions are no
longer purely d-d.

Ligand Field
 Selection Rules
Selection rules determine the probability (intensity) of the transition.

Symmetry (Laporte) Selection Rule: The initial and final

wavefunctions must change in parity.

Spin Selection Rule: The spin of the electron must not change
during the transition.

Transition max (M1cm1)

Spin and Symmetry forbidden "d-d" bands 0.02 - 1

Spin allowed and Symmetry forbidden "d-d" bands 1 - 10

Spin and Symmetry allowed CT bands 103 - 5 x 104

 Outline
Absorption spectroscopy
Types of transitions
atomic
molecular
d-d transitions
Transition moment
Microstates
Correlation diagrams
Tanabe-Sugano diagrams
Selection rules