6.

Spectra of Transition Metal Complexes: Electronic, IR, EPR

READING: Chapter 19, Sections 19.3 – 19.7; Chapter 6, Sections 6.3, 6.4 & 6.6

6.1. Possible Types of Electronic Transitions in Transition Metal Complexes

Groundstate: Electronically excited state:

structure at energy minimum h×ν Affects: bond angles/lengths
acidity constants
specific bond strengths
→ enhanced reactivity

(Source: “Organometallics”, 2nd Ed., Elschenbroich & Salzer, VCH, 1992)

LF: Ligand field transitions between orbitals of dominant d-character

→ hν absorption across Δ0 (d → d)

MLCT: Metal-to-ligand-charge-transfer: formally an intramolecular oxidation of

the metal (and reduction of the ligand.)

LMCT: Ligand-to-metal-charge-transfer: formally an intramolecular reduction of

the metal (and oxidation of the ligand.)

IL: Inter-ligand transition: n → π∗, π → π∗

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• A typical UV-VIS spectrum of a transition metal complex: [Cr(NH3)6]3+

(Source: “Inorganic Chemistry”, 3rd Ed., Shriver & Atkins, Freeman, 1999)

• How can we correlate the spectral appearance with our knowledge of electronic
structure?

6.2. Spectroscopic Terms of Multi-Electron Atoms

6.2.1. General Background

• Any electron in any given orbital is characterized by 4 unique quantum numbers

n principal n = 1,2,3, …
l angular momentum l = 0,1,2,3, …
ml magnetic ml = 0, ± 1, ± 2, ± 3, …, ± l
ms spin ms = ± ½

• In polyelectronic atoms the motions and spins of the individual electrons are
correlated due to their electrostatic and spin-spin interactions.

Consequences:

a) Only electronic configurations that do not violate the Pauli Principle are allowed.

b) The different arrangements of x electrons occupying y orbitals are not all equal in
energy due to the different electron-electron repulsion energies in these microstates.

→ This leads to electronic fine structure of the atom.

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E.g., the d2 configuration:

• Two electrons can occupy any of the 5 d-orbitals depending on their quantum
numbers ml and ms.

One possible microstate would be:

ml 2 1 0 -1 -2

ms +1/2 +1/2

… Obviously there are many more possible…

6.2.2. Deriving Spectroscopic Terms

• Clearly, there is a finite number of (allowed) electronic configurations for 2 electrons

in 5 degenerate orbitals (and for any x electrons in y orbitals).

• Each unique configuration, called a microstate, is defined by a unique combination

of quantum numbers.

• Individual microstates may have different energies because each represents a different
spatial distribution of electrons within the atom resulting in different inter-electronic
repulsions.

• Microstates of the same energy (degenerate) are grouped together into terms.

• A general term symbol that uniquely describes a specific electronic configuration

looks like this:
(2S+1)
LJ
where 2S + 1 is the spin multiplicity (and S is the total spin angular momentum.)
L is the total orbital angular momentum
J is the total angular momentum (spin + orbital)

S = 0 → “Singlet” S = ½ → “Doublet” S = 1 → “Triplet” etc.

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• Microstates can be visualized through the vector model of the atom (cf. CHEM364)

→ Each electron has an orbital angular momentum l and a spin angular momentum s.

• The individual angular momenta (and hence the total angular momentum) can only
have certain orientations → quantization.

(Source: “Molecular Symmetry and Group Theory”, R.L. Carter, Wiley, 1998)

• The total orb. ang. mom. of a group of electrons in an atom is given by some vector
sum of the individual orb. ang. mom. Two simple examples are p2 and d2:

(Source: “Molecular
Symmetry and Group
Theory”, R.L. Carter,
Wiley, 1998)

110
• The total angular momentum J is related to the energy, i.e. different combinations of l
and s will result in different energies or terms.→ SPIN-ORBIT COUPLING!

• There are two ways of defining J:

1) Russel-Saunders coupling:

- Couple all individual orbital angular momenta l to give a resultant total orbital
angular momentum L. (L = Σl)

- Couple all individual spin angular momenta s to give a resultant total spin angular
momentum S. (S = Σs)

- Finally couple L and S to give the total angular momentum J for the entire atom.

- Russel-Saunders coupling works well for the light elements up to bromine.

2) j-j coupling

- Couple individual orbital l and spin s angular momenta first to the complete electron
angular momentum j. (j = l + s)

- Couple all j to give the total angular momentum J. (J = Σj)

- j-j coupling is much more complicated to treat, but should be used for elements heavier
than bromine.

Applying the Russel-Saunders Scheme:

• Need to know the values of L and S:

L = total orbital angular momentum quantum number associated with collection of

microstates with L.

S= total spin angular momentum quantum number associated with collection of

microstates with S.

→ L and S define the spectroscopic term.

L = maximum ML S = maximum MS
ML = 0, ±1, ±2, …, L MS = S, S-1, S-2, …, -S
and

ML = Σ ml MS = Σ ms
where ml and ms are values for individual electrons in a given microstate

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In order to find the terms L and S we have to sum up ml and ms of all possible
microstates.

• There are 2L+1 possible orientations of L and 2S+1 possible orientations of S.

Therefore, the total number of microstates in one term given L and S will be

(2L + 1) × (2S + 1)

• This must be so as the possible values of ML and MS are:

ML = 0, ± 1, ± 2, …, ± L MS = S, S –1, S-2, …, -S

and L = max. ML and S = max. MS

• By convention the atomic term symbols are assigned as follows (function of L and S):

L 0 1 2 3 4 5 6
S P D F G H I
S 0 ½ 1 3/2 2 5/2 6
2S+1 1 2 3 4 5 6 7

Example of a Many Electron Atom: Carbon in its ground-state [He]2s22p2

First an important realization:

• Closed (sub)shells make zero contribution to angular momentum. If all orbitals are
filled with 2 electrons, S = 0 and L = 0 → i.e., all ang. momenta CANCEL OUT!

for [He]2s22p2 that leaves the p2 configuration to be considered.

Each p electron can have:

n = 2, l = 1 (2p orbitals)
ml = 1, 0, -1 (3 possible values: px, py, pz)
ms = ½, - ½
n!
Determining the number of microstates: # microstates =
e! h!
n = total # sites available (i.e., 2 x # of orbitals)
e = number of electrons
h = number of holes (i.e., n – e)

For p2, all possible combination of 2 electrons gives 6!/2!4! = 15 combinations, which
are best collected and visualized in a table:

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 mlms
1 ½ x x x x x
-½ x x x x x
0 ½ x x x x x
-½ x x x x x
-1 ½ x x x x x
-½ x x x x x
ML = Σml 2 1 1 0 0 1 1 0 0 0 -1 -1 -1 -1 -2
MS = Σms 0 1 0 1 0 0 -1 0 -1 0 1 0 0 -1 0

• The total angular momentum quantum numbers L and S are the largest possible
values of ML and MS

• We now have to consider that just as for l and ml, ML and MS can have
ML = L, L-1, L-2, …, -L
i.e. ML = 0, ± 1, ± 2, …, ± L; for any given L there are 2L+1 microstates
and
MS = S, S-1, S-2, … -S
i.e. MS = 0, ±1, ± 2, …, ± S; for any given S there are 2S+1 microstates

• Now start with the maximum ML: We see from the table that the maximum ML
here is 2, and that it only occurs in combination with MS = 0.

→ Therefore, we must have a term with L = 2 and S = 0: 1D

This term accounts for (2L + 1)(2S + 1) = 5 (ML,MS) microstates (2,0), (1,0), (0,0), (-1,0),
(-2,0) and leaves ten microstates to be accounted for.

• Cross off the five microstates that we have accounted for and we are left with:

ML 1 0 1 1 0 0 0 -1 -1 -1
MS 1 1 0 -1 0 -1 0 1 0 -1

• The maximum value of ML is now 1, and it occurs with a maximum MS = 1:

→ Therefore, we must have a term with L = 1 and S = 1: 3P

This term accounts for nine microstates (1,1), (1,0), (1,-1), (0,1), (0, 0), (0,-1), (-1,1), (-
1,0), (-1,-1) and leaves only one microstate (0,0) to account for:

→ Therefore, we must have a term with L = 0 and S = 0: 1S

Each term (1D, 3P, and 1S) defines a state (group of microstates of the same energy.)

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Total Angular Momentum in Many Electron Atoms: Finding J and MJ

Applying the Russel-Saunders Scheme: to our C example…

• As the carbon atom is a light atom we can now use the Russell-Saunders coupling
scheme to account for spin-orbit coupling and its effects.

• Considering only the 9 microstates of the 3P term we find the values of J. Again we
will use a table to visualize the possible combinations:
ML MS MJ
1 1 2
1 0 1
1 -1 0
0 1 1
0 0 0
0 -1 -1
-1 1 0
-1 0 -1
-1 -1 -2

The largest MJ = 2, i.e. the largest J = 2; there are 2J+1 = five states: MJ = 2, 1, 0, -1, -2

If we cross these MJ values off the above table, we are left with:

• The largest remaining MJ =1, therefore J=1: there are three MJ states: 1, 0, -1

• Finally, all that is left is MJ = 0, therefore J=0: there is only one MJ state: 0

→ The term 3P consists of three terms with different total angular momenta:
3 3 3
P2 P1 P0

Each of the terms is degenerate by (2L+1)(2S+1) = (2J+1) giving the total 15 microstates
we started with:

(2J+1)
1
So 1
1
D2 5
3
P2 5
3
P1 3
3
P0 1

Total 15

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The graphs below give a graphical summary of the whole process.

Source: Purcell & Kotz, Inorganic Chemistry, 1977; P.W. Atkins, Physical Chemistry,
3rd Edition, 1987

Let’s derive the term symbols of an electronic configuration that is actually relevant to
the spectra of transition metal ions: d2 (e.g. Ti2+ or V3+).

In how many ways can one arrange two electrons in 5 degenerate orbitals while
obeying the Pauli Principle?

MS
ML -1 0 +1
+ -
+4 (2 ,2 )
+3 (2-,1-) (2+,1-), (2-,1+) (2+,1+)
+2 (2-,0-) (2+,-0-), (2-,0+) (2+,0+)
(1+,1-)
+1 (2-,-1-), (1-,0-) (2 ,-1-), (2-,-1+)
+
(2+,-1+), (1+,0+)
(1+,0-), (1-, 0+)
0 (1-,-1-), (2-,-2-) (1+,-1-), (1-, -1+) (1+,-1+), (2+, -2+)
(2+,-2-), (2-,-2+)
(0+,0-)
-1 to -4 reflection of upper
half

115
Largest value of L:

L = max. ML = 4; forces S = 0 → Term 1G

There will be (2 × 4 + 1) × (2 × 0 + 1) = 9 microstates that have the term symbol 1G.

Second largest value of L:

L = max. ML = 3; S = 1, 0, -1 → Term 3F

There will be (2 × 3 + 1) × (2 × 1 + 1) = 21 microstates that have the term symbol 3F.

… etc. for other values of L and S.

• The complete table of possible terms:

1
G 9
3
F 21
1
D 5
3
P 9
1
S 1
Total # of microstates in d2 45

• The relative energies (and the groundstate) of these terms can be found using Hund’s
Rules:

1) The term with the highest multiplicity (= microstates with highest number of unpaired
electrons) is lowest in energy.

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

Classical explanation: The higher L, the better correlated the orbital motion of the
electrons, the less repulsion, the lower the energy.

→ For the d2 configuration term energies we find the theoretical order:

3
F < 3P < 1G < 1D < 1S

• Experimentally found is:

3
F < 1D < 3P < 1G < 1S

→ Hund’s rules are not always reliable regarding the largest L term,

but are always reliable in establishing the ground state.

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 • How to quickly find the ground state:

- Find the microstate with the highest multiplicity.

- Find the highest possible ML for that microstate

→ Groundstate term.

• Finding the ground state in free ions – e.g. d4 and d7:

ms = +1/2 +1/2 +1/2 +1/2 ms = +1/2 -1/2 +1/2 -1/2 +1/2 +1/2 +1/2

ml = +2 +1 0 -1 -2 ml = +2 +1 0 -1 -2

MS = 1/2 + 1/2 + 1/2 +1/2 = 2 MS = 1/2-1/2 + 1/2-1/2 + 1/2 +1/2 +1/2 = 3/2
ML = +2 + 1 + 0 + -1 =2 ML = +2 + 2 + 1 + 1 + 0 + -1+ -2 =3
so... L = 2; S = 2 so... L = 3; S = 3/2
5
D 4
F

NOTE: Rule #3. For less than half-filled sub-shells, the term with the lowest value of J is
lowest in energy.

Applications of term symbols:

a) Term symbols allow a quick energetic ordering of atomic microstates (Hund’s Rules):

b) Spectroscopic selection rules tell us which transitions are expected to have zero
intensity based on the harmonic oscillator approach.

• Selection rules for electronic transitions can be expressed using term symbols:

ΔS = 0 (electrons are fermions with half-integral spin; photons are bosons with
integral spin → light cannot affect spin)

ΔL = 0, ± 1 with Δl = ± 1

(the orbital angular momentum of an electron must change, but this does
not necessarily affect the overall momentum)

ΔJ = ± 1, 0 (but J = 0 cannot combine with J =0)

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6.2.3. Racah Parameters

• Quantitatively, the repulsion energies between electrons in different terms can be

expressed through the Racah parameters A, B, and C.

• A, B, and C are linear combinations of Coulomb and exchange integrals and can, in
principle, be calculated through quantum mechanical formalisms.

• In practice, they are determined from gas-phase atomic spectroscopy and are always
positive (because they represent repulsions.)

• For our d2 example they are:

E(1S) = A + 14B + 7C ← energy of the 1S term

E(1G) = A + 4B + 2C

E(1D) = A – 3B + 2C

E(3P) = A + 7B

E(3F) = A – 8B

• Actual values of A, B, and C are determined by fitting experimental energies E (from

spectroscopy) to these equations (here: 3 unknowns, 5 equations).

• A is common to all terms (for any d-configuration) and therefore irrelevant for the
relative energies of the terms. i.e., we do not need to know its value!

• If C > 5B the same energetic ordering emerges as found through Hund’s Rules.
If C < 5B Hund’s Rules fail, but the ground state is still correctly assigned.

• Typical values of B and C are: B ≈ 1000 cm-1 C ≈ 4B

• Some real values of some d-block ions in cm-1. (Values in brackets = C/B)

Metal +1 +2 +3 +4
Ti 720 (3.7)
V 765 (3.9) 860 (4.8)
Cr 830 (4.1) 1030 (3.7) 1040 (4.1)
Mn 960 (3.5) 1130 (3.2)
Fe 1060 (4.1)
Co 1120 (3.9)
Ni 1080 (4.5)
Cu 1240 (3.8)

118