Ligand Field Theory

Part I
Assoc. Prof. Preeyanuch Sangtrirutnugul
Department of Chemistry, Faculty of Science
Mahidol University

12 September 2021

1
Objectives
Hour 1:
• Crystal Field Theory
• d-orbital splitting diagrams of octahedron, square-based pyramid, square planar,
tetrahedron complexes

Hour 2:
• Ligand Field Theory
• LFSE, spin configurations, color of T.M. complexes (from d-d transition)

Hour 3:
• Atomic Term Symbols: quantum numbers, ground state terms, microstates
• Molecular Term Symbols
2
Objectives
Hour 1:
• Crystal Field Theory
• d-orbital splitting diagrams of octahedron, square-based pyramid, square planar,
tetrahedron complexes

Hour 2:
• Ligand Field Theory
• LFSE, spin configurations, color of T.M. complexes (from d-d transition)

Hour 3:
• Atomic Term Symbols: quantum numbers, ground state terms, microstates
• Molecular Term Symbols
3
 Crystal Field Theory (CFT)
• Developed by Bethe & van Vleck
• Model: a ligand lone pair is considered a point of negative charge that repels
electrons in the d orbitals of the metal ion (100% electrostatic model).
• Metal-ligand repulsion splits d orbitals into groups -> accounting for UV-vis
spectra, unpaired electrons (magnetic properties), and stability.

d orbitals:

4
 “e-e repulsion and symmetry of d orbitals & ligand positions produce d-orbital splitting”

Crystal field splitting does not change

the total energy of the system.

https://chem.libretexts.org/Courses/Saint_Marys_College_Notre_Dame_IN/CHEM_431%3A_Inorganic_Chemistry_(Haas)/CHEM_431_Readings/11%3A_Ligand_Field_Theory_(LFT)_and
_Crystal_Field_Theory_(CFT)_of_Octahedral_Complexes/11.01%3A_Introduction_to_Crystal_Field_Theory_(Octahdral_complexes) 5
 Uniform field - Octahedral
Free ion field
- - -
- -
M M - -
- -
-
-
z2 x2-y2
eg

+
= 10 Dq

t2g
xy xz yz

• The low energy set has t2g symmetry and are stabilized by -0.4Do each.
• The high energy set has eg symmetry and are destabilized by +0.6Do each.
• The total energy of the d-orbitals is the same as in the uniform field:
0 = (2)(+0.6Do) + (3)(-0.4Do) 6
 Character Table (Oh)
Oh E 8C3 6C2 6C4 3C2(=C4 2) i 6S4 8S6 3Sh 6Sd
A1g 1 1 1 1 1 1 1 1 1 1 x2 + y2 + z2

A2g 1 1 -1 -1 1 1 -1 1 1 -1
Eg 2 -1 0 0 2 2 0 -1 2 0 (2z2 - x2 - y2, x2 - y2)
T1g 3 0 -1 1 -1 3 1 0 -1 -1 (Rx, Ry, Rz)
T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xy, xz, yz)
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
T2u 3 0 1 -1 -1 -3 1 0 1 -1

I Character
E 12C5 table tells
12C5 2 groups
20C3 of symmetry
15C 2 (orbitals with the same energy) but
A not
1 relative
1 energies.1 These 1 have1 to be determined x2 by
+ y2inspection
+ z2 of symmetry.
1 1
T1 3 2 (1 + 25) 2 (1 - 25) 0 -1 (x, y, z), (Rx, Ry, Rz)
7
1 1
T2 3 2 (1 - 25) 2 (1 + 25) 0 -1

G 4 -1 -1 1 0
H 5 0 0 -1 1 (xy, xz, yz, x2 - y2, 2z2 - x2 - y2)
 Possible electron configurations for octahedral dn transition metal complexes (n = 1–10)

If Δo is less than the spin-pairing energy, a high-spin configuration results.

Conversely, if Δo is greater, a low-spin configuration forms.
Q: Write the electronic configurations in terms of t2gxegy of d3, low-spin d4, high-spin d7, d9.
https://chem.libretexts.org/Courses/Saint_Marys_College_Notre_Dame_IN/CHEM_431%3A_Inorganic_Chemistry_(Haas)/CHEM_431_Readings/11%3A_Ligand_Field_Theory_(LFT)_and
_Crystal_Field_Theory_(CFT)_of_Octahedral_Complexes/11.01%3A_Introduction_to_Crystal_Field_Theory_(Octahdral_complexes) 8
 T E 4C3 4C32 3C2
A 1 1 1 1 x2 + y 2 + z 2
1 e e* 1
E e f (2z2 - x2 - y2, x2 - y2)
1 e* e
Character Table (Td)
1
T 3 0 0 -1 (Rx, Ry, Rz), (x, y, z) (xy, xz, yz)

e = e(2pi)>3

Td E 8C3 3C2 6S4 6Sd

A1 1 1 1 1 1 x2 + y2 + z2
A2 1 1 1 -1 -1
E 2 -1 2 0 0 (2z2 - x2 - y2, x2 - y2)
T1 3 0 -1 1 -1 (Rx, Ry, Rz)
T2 3 0 -1 -1 1 (x, y, z) (xy, xz, yz)

Th E 4C3 4C32 3C2 i 4S6 4S65 3Sh

9
Ag 1 1 1 1 1 1 1 1 x2 + y 2 + z 2
Au 1 1 1 1 -1 -1 -1 -1
1 e e* 1 1 e e* 1 (2z2 - x2 - y
 Tetrahedral Crystal Field
Tetrahedral Crystal Field Splitting

opposite splitting of
octahedral field

L
z t2 orbitals point more directly at d orbitals pointing
L ligands and are destabilized. between the axes
y (i.e., dxy, dxz, dyz) are
M
closer to L and more
destabilized.
x L
L
barycenter
(spherical field)
e orbitals point less directly at ligands
and are stabilized.
For the same Mn+ and
Δt < Δo because only 4 ligands and d orbitals point between ligands L, Dt = 4/9 Do10
 Tetrahedral Crystal Field
Uniform field
- Tetrahedral
Free ion -
field
- M - -
M
- -
-
xy xz yz
t
+

-
e
z2 x2-y2

• The low energy set has e symmetry and are stabilized by -0.6Dt each.
• The high energy set has t symmetry and are destabilized by +0.4Dt each.
• The total energy of the d-orbitals is the same as in the uniform field:
0 = (3)(+0.4Dt) + (2)(-0.6Dt) 11
 Small Group Activities 1
(20 minutes)
Based on CFT, draw d-orbital splitting diagrams for:
(1) square-based pyramidal complex and (2) square planar complex

L L
L L L L L L
M M M
L L L L L L
L

12
Objectives
Hour 1:
• Crystal Field Theory
• d-orbital splitting diagrams of octahedron, square-based pyramid, square planar,
tetrahedron complexes

Hour 2:
• Ligand Field Theory
• LFSE, spin configurations, color of T.M. complexes (from d-d transition)

Hour 3:
• Atomic Term Symbols: quantum numbers, ground state terms, microstates
• Molecular Term Symbols
13
 Ligand Field Theory (LFT)
A simpler model than MO theory. LFT focuses on how the d-orbitals of a metal ion interacts
with ligand orbitals to create bonding, antibonding, and non-bonding interactions.

Q: From the above figure, draw bonding, antibonding, and non-bonding interactions.

14
Figure 21.13

15
 330

Consider the series below: 330

What determines the magnitude
Consider of Do ?below:
the series And what properties 330 of the transition

metal complexes
Complex are Consider
affectedthe
byseries
Do ? below:
∆o (in cm-1)
2+ -1
Complex
[Co(H 2O)6] ∆o (in cm
9,000 Co(II))
2+ -1
Complex
[Co(H 2O)6] ∆9,000
o (in cm )
Co(II)
2+
[Co(H
[Co(H22O) O)66]] 3+ 9,000
18,000 Co(II)
Co(III)
3+
[Co(H2O)6] 18,000 Co(III)
3+
[Co(H
[Co(NH 2O) 3)66]]
2+ 18,000
12,000 Co(III)
Co(II)
2+
[Co(NH3)6] 12,000 Co(II)
2+
[Co(NH
[Co(NH33))66]] 3+ 12,000
22,000 Co(II)
Co(III)
[Co(NH3)6] 3+ 22,000 Co(III)
3+
[Co(NH 3 )6 ] 22,000 Co(III)
-------------------------------------------------------------------
III
[Co F6] 3-
-------------------------------------------------------------------
13,000 weak field
III 3-
-------------------------------------------------------------------
[Co F6] 13,000 Co(III)
weak field
III 3-
[Co F6] 13,000 weak
Co(III) field
[CoIII(CN)6] 3- 32,000 Co(III)
strong field
III 3-
[Co (CN)6] 32,000 Co(III)
strong field
III 3-
[Co (CN)6] 32,000 strong
Co(III)field 16
Compare the same oxidation states and then Co(III)
look at the
Compare
ligand type.the same oxidation states and then look at the
Compare
ligand type. the same oxidation states and then look at the
17
s

Ligand (Crystal) Field Stabilization Energy (LFSE/CFSE)

-How much energy is changed relative to a hypothetical spherical crystal field (due to d-orbital splitting).
-For Oh complexes, each t2g and eg electron is assigned the energy of -2/5 Do and +3/5 Do, respectively.

gu- Weak Free Strong

field ion field Weak field: LFSE = 4*(-2/5 Do) + 2*(+3/5 Do )
ak- = -0.4 Do
ken
cal
lex Strong field: LFSE = 6*(-2/5 Do) + 0*(+3/5 Do ) + 2 P
irs. High = -2.4 Do + 2 P
no spin
ing Low
spin P = (electron) Pairing energy
the
do
**Pairing energies taken into account when the pairing of electrons are
ues
additional to the pairing that occurs in the spherical field (free ion case).
air-
18
E is Figure 20.5 The effect of weak and strong
the ligand fields on the occupation of orbitals
for a d6 complex. The former results in a
ing high-spin configuration and the latter in a
 in the number
nfiguration.
in t2g and two
n, with all five
d1 through d10, Pairing Energy (P)
Two factors:

(1) e-/e- repulsion : Pcoul (destabilized, positive E)

octahedral
(2) Loss of exchange energy (of the same spin, same E e-s) Pex (stabilized, negative E)

The five c
4 5
r. The
exchange.
P = Pcoul + Pex
1 1 2 3
ons with the
the exchange
Note: Heavier TMs give low spin since orbitals are more diffuse, pairing energy is usually small.
changeable
1 1 2 2 3 3
ontribution. 19

h-spin and as
Using LFSE and P to predict spin configuration of complexes
General ideas on how to assign low-spin (L.S.) or high-spin (H.S.) configurations:
Compare the values of Do and pairing energy Do > P -> L.S. configuration
Do < P -> H.S. configuration

Complex ion Do (kJ mol-1) P (kJ mol-1) Spin

configuration
Fe(H2O)62+ 124 211
Fe(CN)64- 395 211
CoF63- 156 251
Co(NH3)63+ 275 251

Small group activities: Calculate LFSE of Fe(H2O)62+ and Fe(CN)64-

20
 Electronic transitions of Oh d1 complex

OH2
(all are
e
six-coordinates)
e
338

H 2O OH2
3+ g g
• Promoting an electron in Oh d1 complex
Ti hν
H 2O OH2 Δo Δo from g.s. to e.s. (t2g1eg0 -> t2g0eg1)
OH2 t2g t2g requires energy equal to Do (~ hn).
d1 complex
Simplistically, you may want to view the promotion of
an electron from the t2g to the eg level as the basis for
the hv absorption peak. In the case of t2g1eg0
e 2O)6]3+, this is “sort of ” correct. In
compounds [Ti(H
other words the energy, hv, will be very similar to ∆o.

Realistically, transitions occur between “states” and not

“orbitals” t2g1eg0 can be defined by a state symbol, -1 3+?
Small Group Activities:
called a term symbol. Light absorbed at ~ 20 300 cm , which color is Ti(H 2O) 6
21
 Electronic Spectroscopy
Intro to Spectroscopy
The color we observe for complexes is a direct result of light
absorption and its complementary transmission
Observed Color Light Absorbed Abs Wavelength / nm
colorless UV < 380
yellow violet 380-450
orange blue 450-490
red green 490-550
violet yellow 550-580
blue orange 580-650
green red 650-700
colorless IR > 700

When a compound absorbs light in the UV-vis-NIR region, an electron

moves from a low energy orbital to a higher energy orbital
• UV-vis-NIR spectroscopy is a probe for electronic structure
hc wavenumber (cm–1) = λ–1
E h hc
frequency (Hz) 22
wavelength (nm)
 Jahn-Teller Theorem
J-T theorem: There cannot be unequal occupation of orbitals with identical energies. If
so, the molecule distorts to remove that degeneracy, consequently lowering energy.

Ex. Cr2+, Mn3+ vs.

Other Oh complexes with J-T distortion:

L.S., d7 d9
Tetragonal distortion (Co2+, Ni3+) (Cu2+)
(more common) z2
½ d1
d1
x2-y2 ½ d1
elongate compress
xz yz
along z along z ⅓ d2
d2
d1 >> d2 ⅔ d2 23
xy
 Evidence of J-T Effect
(1) Spectroscopic UV-Vis of Ti(H2O)63+: (2) Bond lengths of Cu(NH3)62+:
t2g1eg0 t2g0eg1

NH3 2+
H 3N NH3
Cu Cu—N: 2.67 Å
H 3N NH3
NH3 Cu—N: 2.07 Å

cm-1

d electron vs. J-T effect:

# of d electron 1 2 3 4 5 6 7 8 9 10
High Spin s w w
w w s
Low Spin w w s
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 Small Group Activities 2
(20 minutes)
(1) Calculate LFSE of Fe(H2O)62+ and and Fe(CN)64- (Slide 20).
(2) Calculate the wavelength of light absorbed by Ti(H2O)63+ and predict its color (Slide 21).

25
Objectives
Hour 1:
• Crystal Field Theory
• d-orbital splitting diagrams of octahedron, square-based pyramid, square planar,
tetrahedron complexes

Hour 2:
• Ligand Field Theory
• LFSE, spin configurations, color of T.M. complexes (from d-d transition)

Hour 3:
• Atomic Term Symbols: quantum numbers, ground state terms, microstates
• Molecular Term Symbols
26
 den’ transition. Next are two bands with intermediate intensities; these are ‘spin-a
transitions between the t2g and eg orbitals of the complex, which are mainly deriv
[V(OH ) ]
the metal d orbitals.
2 6 The
3+third feature in the spectrum is an intense charge-transf
at short wavelength (labelled CT, denoting ‘charge transfer’), of which only the low
Hexaaquavanadium(III) istailan octahedral
is evident d2 metal complex.
in the illustration.
Electronic transitions of Oh d3 complex
NH3 3+ 4
H 3N NH3
Cr
H 3N NH3 ground state
NH3 2 1 3
electron configuration CT t2g eg t2g

log(ε / dm3 mol–1 cm–1)

d3 complex
4 4 4 4
{dz2, dx2–y2} 2 T1g A 2g T2g A 2g
eg
2 4
3T Eg A 2g
1g Magnified
absorption
Figure 20.23 The spectrum of the d3 0
complex [Cr(NH3)6]3+, which illustrates the
{dxy, dand
eatures studied in this section, xz, the
dyz} 200 400 600 800
assignments of the transitions as explained t2g (50 000) (25 000) (17 000) (12 500)
~ / cm-1)
λ / nm (ν
n the text.

For open-shelled multi-electron systems, electronic transitions occur

between electronic states, not orbitals!
27

h20.indd 530
 Atomic Energy States & Term Symbols
• Due to e-e repulsion, one electronic configuration may result in several atomic energy states.
• Luckily, an atom’s electronic state depends entirely on its unfilled subshells.

Russel-Saunders (LS) coupling scheme:

Spin degeneracy or multiplicity

Term Symbol: 2S+1 LJ

L = total orbital angular momentum QN (Σl); S = total spin QN (Σms);

J = Russel-Saunders spin-orbit coupling = l+S, l+S-1, …, |l–S|

28
 Atomic Quantum Numbers
-Quantum numbers L and S describe collections of microstates.
-ML and MS describe the microstates themselves.
-L and S are the largest possible values of ML and MS.

L = 0 : S state
ML
L = 1 : P state
Ms
L = 2 : D state
S = |ms1 + ms2|, |ms1 + ms2 - 1|, …., |ms1 - ms2|
L = 3 : F state
Atomic States Individual Electrons
8/14/2021 8.8.1 https://chem.libretexts.org/@go/page/210846
ML = 0, +1, +2, …, + L ml =0, +1, +2, …, + l
MS = S, S-1, S-2, …, -S ms = +1/2, -1/2
29
 Q: Fill in the appropriate values:

Term L S J value(s)
L = 0 : S state 1S

L = 1 : P state 2S

L = 2 : D state 3P 1 1
L = 3 : F state 2 3/2
3 5, 4, 3, 2, 1

30
• For a one-electron atom or ion, s p d f orbitals correlate to term symbols S, P, D, F,
• Term symbols for the 11 possible dn systems are:

dn Term Symbol(s)
d1 or d9 2D

d2 or d8 1S, 1D, 1G, 3P, 3F

d3 or d7 2P, 2 2D, 2F, 2G, 2H, 4P, 4F

d4 or d6 2 1S, 2 1D, 1F, 2 1G, 1I, 2 3P, 3D, 2 3F, 3G, 3H, 5D
d5 2S, 2P, 3 3D, 2 2F, 2 2G, 2H, 2I, 4P, 4D, 4F, 4G, 6S
d0 or d10 1S

Ground state term symbols in red

31
How to assign the lowest energy state (ground state)?
For the ordering of the energy of
(1) Term symbol with the highest spin multiplicity free ion terms, we consider
Racah parameters (p. 535).
(2) Term symbol with the highest L
(3) When J values are present, the less than half-filled configurations -> |L-S|
the more than half-filled configurations -> L+S

Q: What is the ground state term symbol for (1) Ti3+ (2) Cr3+ (3) Mn2+ ions?

32
 Molecular Term Symbols
Describe overall electronic orbital state of the complex.

4A A = non-degenerate state
2g E = doubly degenerate
Multiplicity = T = triply degenerate
3 unpaired electrons + 1
=4
eg

Non-degenerate
ground state =

t2g A
33
 Symmetry Labels for Configurations
Electron configurations have symmetry labels that match their degeneracies, as follows:

T designates a triply degenerate

asymmetrically occupied states.

E designates a doubly degenerate

asymmetrically occupied states.

A or B designates a nondegenerate state.

Each set of levels in A or B state is
symmetrically occupied.

Ex. Identify the following configurations as T, A, or E states in Oh complexes:

a) t2g6eg1 b) t2g6eg2 c) t2g2
34
Electronic States Arising from the Oh and Td Ligand Fields

Russell-Saunders Oh Crystal Field Components Td Crystal Field Components

Terms (Free ions)
S A1g A1
P T1g T1
D Eg + T2g E + T2
F A2g + T1g + T2g A2 + T1 + T2
G A1g + Eg + T1g + T2g A1 + E + T1 + T2
H Eg + T1g + T1g + T2g E + T1 + T1 + T2
I A1g + A2g + Eg + T1g + T2g A1 + A2 + E + T1 + T2

35
 Small Group Activities 3
(20 minutes)
Derive a microstate table and all free ion term symbols for electron configuration d2
How many microstates?
Identify the ground state term symbol.

36