Electronic Spectroscopy of Transition Metal Complexes: (Ti (OH) ) D Ion, Octahedra

Electronic Spectroscopy
of
Transition Metal Complexes
© K. S. Suslick, 2013
Absorption of Light
blue (400-490 nm)
[Ti(OH2)6]3+ = d1 ion, octahedra white light
yell.-gr (490-580 nm)
400-800 nm
red (580-700 nm)
blue
red }
} }}
This complex appears light purple

because it absorbs green light.
 in nanometers
max = 510 nm
1
d-d Transitions:
d1 – d9 of M(OH2)6n+ d5 x100 rel.
d1
d2 d6 x2.5 rel.
d7
d3 d8
d9
d4
same
ε scale
except
d5,& d6.
d-d Transitions vs. Coord. Geometry

High Spin FeII, d6
6 coord
5 coord
sq pyr
5 coord
trig bipyr
4 coord
2
What is electronic spectroscopy?
Absorption of radiation leading to electronic transitions
within a metal complex.
[Ru(bipy)3]2+ [Ni(H2O)6]2+
104
10
Absorption
Absorption
200 400 700 ~14 000 25 000 50 000

nm (wavelength)  cm-1 (frequency)

UV visible visible UV
UV = higher energy transitions: between ligand orbitals

visible = lower energy transitions: between d-orbitals of transition metals
or between metal and ligand orbitals
Energy of Transitions
Excited State
electron transitions
higher energy
(100 - 104 kJ mol-1)
visible and UV radiation Ground State
molecular rotations
lower energy
(0.01 - 1 kJ mol-1)
microwave radiation
During an electronic transition molecular vibrations
the complex absorbs energy medium energy
an electron changes orbitals (1 - 120 kJ mol-1)
the complex changes energy state IR radiation
the structure changes slightly
3
Characteristics of Absorption Spectra
1. Number of peaks
This depends on the electron configuration of the metal center.
2. Energy: what wavelength or frequency
Depends on the ligand field splitting parameter, oct or tet,
and on the degree of inter-electron repulsion.
3. Intensity
This depends on the "allowedness" of the transitions, which is
described by two “selection rules.”
Measurement of Absorption Spectra: Beer’s Law
A = l)(C)
ε is the extinction coefficient, measure of absorption cross-section
l, is semi-obvious - the pathlength of the light
C, also semi-obvious - the concentration of the sample
Extinction Coefficients
 is the extinction coefficient, i.e., cross-section for photons
has units: usually in M-1 cm-1
Large : allowed Transition

Small : partiallly allowed (spin or symmetry forbidden)
Very small : “forbidden” (both spin and symmetry forbidden)
 >1000 Charge transfer: spin and symmetry allowed
1000 – 10 Spin Allowed– d-d transitions in non-Oh (tetrahedral…)
10 – 1 Spin allowed, symmetry forbidden: Oh
<1 Spin Forbidden, Symmetry Forbidden

4
d-d and Charge Transfer Transitions
Types of Electronic Transitions in TM Complexes

d-d: usually in the visible region
relatively weak,  ~ 1 – 100 if spin allowed
< 0.1 if spin forbidden
energy varies with ∆o (or ∆t)
LMCT: Ligand to Metal Charge Transfer

h
σL or πL d*
very intense, generally in UV or near UV
MLCT: Metal to Ligand Charge Transfer

h
d* πL
very intense ( ~ 100 – 10,000)
needs π-acceptor Ligand (CO, CN–, …
LL: Ligand to Ligand
πL h πL*
very intense ( ~ 100 – 10,000)
h
Rydberg: localized MO high energy,
© K. S. Suslick, 2013 highly delocalized, deep UV
5
Ligand Field Splitting of d-orbitals
Know these by heart!

Ligand Field Splitting of d-orbitals
6
d Orbitals in a Ligand Field
• There are 5 d-orbitals; they have different shapes

(and you’d better know them!).
• When you put ligands around the metal ion,
the ligands are Lewis bases,
they donate an electron pair towards the metal.
• That RAISES THE ENERGY OF THE d-ORBITALS!
• The d-orbitals are anti-bonding or at best non-bonding.
• The stability of the bonding comes from the ligand
orbitals being stabilized by delocalization
onto the metal ion (by mixing into the d-orbitals).
• The d-orbitals aren’t all the same in how much
they feel the ligand lone pairs.
d Orbitals in a Octahedral Ligand Field

Let’s consider d-orbitals in an octahedral complex:
i.e., an octahedral “Ligand Field”.
The 6 ligands are put on the x, y, z axes (black dots below)
Two d-orbitals are pointing right at the ligands (anti-bonding).
Three d-orbitals are pointing in-between ligands (nonbonding).
Antibonding d: How do we know eg or t2g?

Character table!
Nonbonding d:
7
Two Kinds of d Orbitals in Octahedral Field
Pointed
eg at
Ligands.
Pointed
t2g between
Ligands.
d orbitals in Oh
d orbitals: z2, x2-y2, xy, xz, yz
No d-orbital is
Note: There are only 5 d-orbitals,
ever x2 + y2 +z2
but there are 6 quadratics!
2z2-x2-y2  dz2
8
d Orbitals in a Tetrahedral Ligand Field
Let’s now consider d-orbitals in a tetrahedral complex:
i.e., an tetrahedral “Ligand Field”.
The 4 ligands are put on corners of cube (black dots below)
Three d-orbitals are pointing right at the ligands (anti-bonding).
Two d-orbitals are pointing in-between ligands (nonbonding).
Antibonding d:
How do we know t2 or e?
Nonbonding d: Character table!
d Orbitals in Td
d orbitals: z2, x2-y2, xy, xz, yz
Why no subscript “g”? No d-orbital is

ever x2 + y2 +z2
2z2-x2-y2 : dz2
9
The Octahedral Ligand Field M.O.s
antibonding
M-L sigma* levels
eg
4 p ( t1u )
4 s ( a 1g )  octahedral field splitting
3d
t2g
group orbitals for L6

(a1g, t1u, eg)
M-L sigma bonding levels
The Tetrahedral Ligand Field M.O.s
antibonding
M-L sigma* levels
4 p ( t2) t2
4 s ( a 1)
t tetrahedral field splitting
3d
e
group orbitals for L4

(a1 , t 2 )
M-L sigma bonding levels
10
The Tetrahedral Ligand Field M.O.s
tet ~ 4/9 oct = 4/9 o 3T 3A

2g
1g
3T
2g
smaller splitting, therefore 3T
2g
usually high spin. 3T
3A 1g
2g
3T 3A
1 2
3T
3T 2
2
3T
3A 1
2
“Real” MOs of Coordination Complexes
The d orbitals are

non-bonding to
antibonding
The stabilization of
these ligand
orbitals is what
holds coordination
complexes
together!
11
“Real” MOs of Coordination Complexes
[Fe Cl6] 3-
dx2-y2 dz2
dxy dxz dyz
π Metal-Ligand Overlap
There is a second kind of overlap of ligand orbitals with d-orbitals
(in Oh, only for dxy, dxz, dyz  d).
No  interactions
possible!
Three kinds of Ligands:

π interaction < σ interaction
1. Non-π σ-donors (i.e., σ bases) π interaction = 0 for non-π
bonding ligands (e.g. NH3)
2. π-donors (i.e., π-bases)
BOTH are ALSO σ-donors!
3. π-acceptors (i.e., π-acids)
12
π-donor (π base) Ligands
d eg
decreases
o
d t2g
high energy p or 
filled orbital
of π Base
π Bases are “weak-field” ligands (e.g., I-, Br-, Cl-, S2-, SCN-).
π Bases decrease d-d splitting relative to σ only donors (e.g., NH3).
π-acceptor (π acid) Ligands
d eg
increases Low Energy *
o empty orbital of π Acid
d t2g
π Acids “back π-bonding” are “strong-field” ligands

(e.g., CO, PF3, PR3, CN-, i.e., low lying * orbitals).
“back π-bonding” means e- flow from filled metal d to empty ligand
*.
π Acids increase d-d splitting relative to σ only donors (e.g., NH3).

13
The Spectrochemical Series: “Tuning the Gap”
eg
eg
I- < Br- < Cl-< OH- < RCO2- < F-
Δ Δ
t2g < H2O < NCS- < NH3 < en < bipy
< NO2- < phen < PR3 < CN- < CO

weak field ligand
(π bases)
high spin complexes In the middle t 2g
(σ only donors) “strong field” ligands
(π acids)
low spin complexes
Octahedral splitting = ∆o is larger for

 High metal ion charge
 Ligands with strong σ donation
 Ligands with weak π donation
 Ligands with strong π acception
 2nd & 3rd Row T.M.
The Spectrochemical Series: “Tuning the Gap”

eg
eg
I- < Br- < Cl-< OH- < RCO2- < F-
Δ Δ
t2g < H2O < NCS- < NH3 < en < bipy
< NO2- < phen < PR3 < CN- < CO

weak field ligand
(π bases)
high spin complexes In the middle t 2g
(σ only donors) “strong field” ligands
(π acids)
low spin complexes
Why does CN− lead to large splitting (big ?

Highly basic: raises energy of eg levels.
-bonding: lowers energy of t2g orbitals, π-back bonding.
In contrast, consider CO:

little σ basicity (not protonated) − mostly -back bonding effect
(i.e., lowers t2g orbitals a lot)
14
d Orbital Splittings vs. Ligand Field Symmetry
xy, z2, (xz yz)

energies
can switch
d Orbital Splittings vs. Ligand Field Symmetry
Oh (octahedral) D4h (tetragon. elong.) C4v (sq. pyram.)
eg b1g x2–y2 b1 x2–y2

z2, x2–y2
a1g z2
a1 z2
t2g xy,xz,yz b2g xy

b2 xy
eg xz, yz e xz, yz
Td (tetrahedral) D4h (sq. planar) D3h (trig. bipyram.)

b1g x2–y2
a’1 z2
t2 xy,xz,yz
b2g xy
e’ x2–y2, xy
e z2, x2–y2 a1g z2
eg xz, yz e’’ xz, yz
xy, z2, (xz yz) energies can switch
15
Ligand Field Splitting of d-orbitals, d1
Analysis of the UV-vis Spectrum of [Ti(OH2)6]3+: h ~ o
2E Simplest case because only one electron
g
ES
energy
eg eg
h
2T
2g o
GS
t2g t2g
bond length
complex in electronic complex in electronic

ground state (GS) the “d-d transition” excited state (ES)
[Ti(OH2)6]3+ max = 510 nm o is  243 kJ mol-1

20,300 cm-1
An electron changes orbital, the ion changes energy state,
and Ti-O bonds elongate.
Ligand Field Splitting of d-orbitals, d1
16
Jahn-Teller Distortions
Jahn-Teller Theorem:
Any system which has a partially-filled degenerate set
of orbitals will undergo a distortion to split that degeneracy
and lower the electronic energy of the system.
J.-T. NEVER tells you what distortion will be best,

ONLY that there MUST be one that will lower the energy.
Jahn-Teller Distortions
17
Other Cases of Jahn-Teller Distortions
Strongest J-T distortions:

d4(H.S.) d7(L.S.) d9
eg
t2g
Jahn-Teller Distortion, d1
18
Limitations of MO Diagrams
V3+ in Al2O3 (octahedral O coordination) = d2 ion
eg
t2g
For the d2 complex we see three bands!

The electronic structure is more complicated than represented by
orbital energies alone.
The problem: orbital energy diagrams ignore inter-electron repulsion,

i.e., several states comprise the (t2g)1(eg)1 configuration,
with different inter-electron repulsion energies.
What are these bands? Are they d-d transitions or …?
19
Use of Tanabe-Sugano Diagrams, d2
So, what’s B?
i.e., Racah parameter
 = 10Dq = ligand field splitting
Use of Tanabe-Sugano Diagrams, d2
10Dq = 
20
Use of Tanabe-Sugano Diagrams
B value (Racah parameter) in Tanabe-Sugano Diagrams
decreases as inter-electronic repulsions decrease
decreases for lower oxidation states,

2nd and 3rd row metals,
larger d orbitals
greater covalency
more polarizable ligand
more polarizable metal
Nephelauxetic Series (“Cloud Expanding”):

 = B in complex
B in Free Ion
F > O > N > Cl > Br > S ~ I > Se
~ 1 ~ 0.3
Use of Tanabe-Sugano Diagrams

V3+ in Al2O3 (octahedral O coordination) = d2 ion
Remember T.-S. diagrams are normalized energies.

For V3+, B = 866 cm-1 and C/B = 3.6 cm-1 (look up, e.g., previous page)
So, E/B of the 3 bands are 20.1, 29.1, 29.9
21
Tanabe-Sugano Diagram for d2 Ions
spin allowed transitions in red
V3+ in Al2O3
E/B = 39.9
29.1
20.1
E/B
So, all three bands
are accounted for
as spin allowed
d-d transitions.
 = 2 B = 17000 cm-1
10 20 30
/B
Tanabe-Sugano Diagram for d2 Ions: Spectra
E/B 
10
[V(H2O)6]3+, d2 Oh
 cm-1

30 000 20 000 10 000
[V(NH3)6]3+
/B
[V(O)6]3-
Gaseous V3+
(in principle 4 transitions [V(H2O)6]3+ (in principle, 10 transitions/
but only 1 is spin allowed)
excited states, but only 3 are spin allowed)
22
d5 Octahedral Case: [Mn(H2O)6]2+
4T
50 000 2(g)
4T
Multiple absorption bands 4F
1(g)
4A
Very low intensities ( 40 000 2(g)
cm-1 4T
Transitions are forbidden 4D 1(g)
4E
30 000 (g)
4P 4T
2(g)
4G 4E , 4A
(g) 1(g)
20 000
4T
2(g)
 4E (G)
g 4T
4A (G) 10 000 1(g)
0.03 1g
4T
2g (D) 6S 6A
500 1000 1(g)
0.02 4T 4E (D)
1g(G) g
Dq (cm-1)
4T
2g (G)
0.01
v / cm-1
20 000 25 000 30 000
d 5 Octahedral Case: [Mn(H2O)6]2+

4T
2(g)
50 000
4T
1(g)
4F
4A
2(g)
40 000
cm-1 4T
1(g)
4D
4E 30kK
30 000 (g)
4T
4P 2(g)
4G 4E , 4A
(g) 1(g)
20 000
4T
2(g)
20kK
4T
1(g)
10 000
6S
o (cm-1)
23
d8 Octahedral Case: [Ni(H2O)6]2+
[Ni(OH2)6]2+ = d8 ion
eg A
t2g
25 000 15 000

 cm-1
For the d8 complex we see at least three bands!

The electronic structure is more complicated than represented by
orbital energies alone.
d8 Octahedral Case: [Ni(H2O)6]2+ vs. Ni(en)32+
24
Selection Rules
Selection rules determine the intensity of electronic transitions
(intensity ~ allowedness)
Spin Selection Rule
S = 0
There must be no change in spin multiplicity during an electronic transition

(for light elements where S is a “good” QN.
Symmetry (a.k.a. Laporte) Selection Rule (essentially dipole change requirement)
l = ± 1
For centrosymmetric systems

there must be a change in parity during an electronic transition: i.e.,
gu
Basically, d-d transitions are forbidden for octahedral complexes.
Selection Rules
Spin Selection Rule
There must be no change in spin multiplicity during an electronic transition.
25
Selection Rules
Orbital Selection Rule
There must be a change in dipole moment during an electronic transition.
Selection Rules
Orbital Selection Rule
There must be a change in dipole moment during an electronic transition.
e.g., for d-orbitals, d = g but µ = u (i.e., x, y, z)
= g  u  g
= u ≠ A1g
So, d-d transitions are orbitally (“LaPorte”) forbidden!
26
Selection Rules
Relaxation of the Laporte Selection Rule.

Tetrahedral vs. Octahedral Complexes
No inversion center in Td, therefore no ungerade vs. gerade!
 
[V(H2O)6]3+, d2 Oh
600 [CoCl4]2-, d7 Td 10
400
5
200
v / cm-1 
 cm-1
25 000 20 000 15 000 10 000 5 000 30 000 20 000 10 000
Spin-allowed; Spin-allowed;
Laporte-allowed Laporte-forbidden
27
Forbidden Transitions
h.s. d5, double-trouble:
• Laporte forbidden
• Spin forbidden
 4E (G)
g
4A (G)
0.03 1g
4T
2g (D)
0.02 4E (D)
4T
1g(G) g
4T
2g (G)
0.01
20 000 25 000 30 000
v / cm-1
Origin of Forbidden Transition Intensities
28
Consider electronic transitions:
It’s not just about

the electronic state:
absorbance
fluorescence
we must also consider

the vibrational sub-states!

Vibronic Coupling:
29
Vibronic Transitions
Vibronic Transitions: Franck-Condon Factor
30
Franck-Condon Principle: nuclear much slower than electron motion.
Corollary: electronic transitions are “vertical” (i.e., nucleus can’t move).
Consequence: overlap between GS vibration and XS vibration matters.
Non-displaced XS
(no big bond changes)

Franck-Condon Principle: nuclear much slower than electron motion.
Corollary: electronic transitions are “vertical” (i.e., nucleus can’t move).
Consequence: overlap between GS vibration and XS vibration matters.
Displaced XS
(no big bond changes)
0-2
0-3
0-4 0-1
0-0
31
Vibronic Coupling Selection Rules
Electronic Transitions: Formaldehyde
200 270
32
µ = B1 + B2 + A1
x y z
Consider the C=O orbitals a1

i.e., the frontier orbitals: b1
b2
a1
b1
a1
1p, 2s, core C, H-C orbitals are lower in energy.

a1
b1
b2
a1
b1
a1
33
a1
b1
b2
a1
b1
a1
a1
b1
b2 This transisiton
a1 is allowed,
but it’s out in
b1 the vacuum UV
a1
34
Vibronic Transitions: H2CO
In summary, 2 transitions observed:
(but where did the forbidden transition get ε =100?!)
So, let’s consider the effect of vibronic coupling on the forbidden 1A2 → 1A1
Vibronic Transitions: H2CO
XXX = A1 (z)
XXX
Hot Bands
(not populated
at RT)
35
Vibronic Transitions: Co(NH3)63+ Oh
Givens: 1. 1A1g G.S. (d6 S = 0)
2. Two electronic XSs,
1T
1g and T2g
1
3. Co-N vibrations (15):

a1g, eg, 2 t1u, t2g, t2u
4. µ = T1u
Is 1A
1g → 1T1g allowed?
µ
T1g  T1u  A1g = A1u + Eu + T1u + T2u i.e., NO A1g !
Vibronic coupling with vibrations t1u and t2u

so some intensity expected (ε ~ 50).
Vibronic Transitions: Co(NH3)63+ Oh

Givens: 1. 1A1g G.S. (d6 S = 0)
2. Two electronic XSs,
1T
1g and T2g
1
3. Co-N vibrations (15):

a1g, eg, 2 t1u, t2g, t2u
4. µ = T1u
Is 1A
1g → 1T2g allowed?
µ
T2g  T1u  A1g = A2u + Eu + T1u + T2u i.e., NO A1g !
Vibronic coupling with vibrations t1u and t2u

so again, some intensity expected (ε ~ 50).
36
Vibronic Transitions: Co(NH3)63+
1T
1g
1T
2g
1A
1g
Other Intensity Stealing Mechanisms
37
Other Intensity Stealing Mechanisms
Charge-Transfer (CT) Transitions
38
Charge Transfer Transitions
d0 and d10 ions have no d-d transitions, BUT often still colored.
Why? Zn2+ d10 ion colorless

TiF4 d0 ion white
TiCl4 d0 ion white
TiBr4 d0 ion orange
TiI4 d0 ion dark brown
[MnO4]- Mn(VII) d0 ion intensely purple
[Cr2O7 ]- Cr(VI) d0 ion bright orange
[Cu(MeCN)4]+ Cu(I) d10 ion colorless

[Cu(phen)2 ]+ Cu(I) d10 ion dark orange
These colors come from excitation of electrons from M-centered orbitals

to Ligand-centered orbitals (or the reverse). MLCT and LMCT.
Selection rules for Charge-Transfer (CT) Bands
CT transitions are spin-allowed and symmetry-allowed
Transitions occur from a Transitions occur between

singlet G.S. to a singlet E.S.: metal based orbitals with d-
S = 0 character and ligand based
orbitals with p-character:
l = ± 1
allowed CT transitions can therefore be

much more intense than d-d transitions.
39
LMCT Transitions
[Cr(NH3)5Cl]2+, Cr(III), d3
2+
LMCT
cm-1)
NH3
H3N NH3
4
Cr
-1
/L mol
H3N Cl
3
H3N
Log (
2
d-d d-d
1
200 400 600  nm

(50 000 cm-1) (25 000 cm-1) (17 000 cm-1)
CT bands can dominate the spectrum!
LMCT Transitions
[Cr(NH3)5Cl]2+, Cr(III), d3
2+
LMCT
cm-1)
NH3
H3N NH3
4
Cr
-1
/L mol
H3N Cl
3
H3N
Log (
d-d d-d
1
200 400 600  nm

(50 000 cm-1) (25 000 cm-1) (17 000 cm-1)
Identifying charge transfer transitions:

• Intensity
• Vibronic fine structure
• Solvatochromism - variation in absorption wavelength with solvent
• Computational modeling
40
LMCT Transitions

• Intensity
• Vibronic fine structure (best at low temp and non-interactive environment)
LMCT Transitions

• Intensity
• Vibronic fine structure (best at low temp and non-interactive environment)
41
Fluorescence vs. Absorbance
Vibrational relaxation (i.e., dropping to =0)

is generally faster than fluorescence
of diamagnetic light element compounds,
but often no fluorescence from TM complexes.
42

Electronic Spectroscopy of Transition Metal Complexes: (Ti (OH) ) D Ion, Octahedra

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Electronic Spectroscopy of Transition Metal Complexes: (Ti (OH) ) D Ion, Octahedra

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Electronic Spectroscopy

This complex appears light purple

d-d Transitions vs. Coord. Geometry

200 400 700 ~14 000 25 000 50 000

UV = higher energy transitions: between ligand orbitals

Measurement of Absorption Spectra: Beer’s Law

Large : allowed Transition

Very small : “forbidden” (both spin and symmetry forbidden)

 >1000 Charge transfer: spin and symmetry allowed

1000 – 10 Spin Allowed– d-d transitions in non-Oh (tetrahedral…)

10 – 1 Spin allowed, symmetry forbidden: Oh

<1 Spin Forbidden, Symmetry Forbidden

Types of Electronic Transitions in TM Complexes

LMCT: Ligand to Metal Charge Transfer

MLCT: Metal to Ligand Charge Transfer

Know these by heart!

Ligand Field Splitting of d-orbitals

• There are 5 d-orbitals; they have different shapes

d Orbitals in a Octahedral Ligand Field

Antibonding d: How do we know eg or t2g?

d orbitals: z2, x2-y2, xy, xz, yz

Why no subscript “g”? No d-orbital is

group orbitals for L6

M-L sigma bonding levels

The Tetrahedral Ligand Field M.O.s

group orbitals for L4

M-L sigma bonding levels

tet ~ 4/9 oct = 4/9 o 3T 3A

“Real” MOs of Coordination Complexes

The d orbitals are

dxy dxz dyz

Three kinds of Ligands:

π Bases decrease d-d splitting relative to σ only donors (e.g., NH3).

π-acceptor (π acid) Ligands

π Acids “back π-bonding” are “strong-field” ligands

π Acids increase d-d splitting relative to σ only donors (e.g., NH3).

< NO2- < phen < PR3 < CN- < CO

Octahedral splitting = ∆o is larger for

The Spectrochemical Series: “Tuning the Gap”

< NO2- < phen < PR3 < CN- < CO

Why does CN− lead to large splitting (big ?

In contrast, consider CO:

xy, z2, (xz yz)

d Orbital Splittings vs. Ligand Field Symmetry

Oh (octahedral) D4h (tetragon. elong.) C4v (sq. pyram.)

eg b1g x2–y2 b1 x2–y2

t2g xy,xz,yz b2g xy

Td (tetrahedral) D4h (sq. planar) D3h (trig. bipyram.)

eg xz, yz e’’ xz, yz

xy, z2, (xz yz) energies can switch

complex in electronic complex in electronic

[Ti(OH2)6]3+ max = 510 nm o is  243 kJ mol-1

Ligand Field Splitting of d-orbitals, d1

J.-T. NEVER tells you what distortion will be best,

Strongest J-T distortions:

For the d2 complex we see three bands!

The problem: orbital energy diagrams ignore inter-electron repulsion,

i.e., Racah parameter

 = 10Dq = ligand field splitting