Q-1 a) Use the concept of ‘Hole Formulation’ and write both ground and

excited states arising from Ni2+ (d8 system). (4)

According to hole formulation, the d8 system will be equivalent to d2 system since d8 = d10-8 =d2

Column 1 2 3 4 5 6 7

mℓ +2 +1 0 -1 -2 ML MS

↑ ↑ 3 1

↑ ↑ 2 1

↑ ↑ 1 1

↑ ↑ 0 1

↑ ↑ 1 1

↑ ↑ 0 1

↑ ↑ -1 1

↑ ↑ -1 1

↑ ↑ -2 1

↑ ↑ -3 1

↑↓ 4 0

↑↓ 2 0

↑↓ 0 0

↑↓ -2 0

↑↓ -4 0

↑ ↓ 3 0

↑ ↓ 2 0

↑ ↓ 1 0

↑ ↓ 0 0

↑ ↓ 1 0

↑ ↓ 0 0
↑ ↓ -1 0

↑ ↓ -1 0

↑ ↓ -2 0

↑ ↓ -3 0

mℓ 4 3 2 1 0 -1 -2 -3 -4

ms 0 0 0 0 0 0 0 0 0

Since ML = 4, ∴ L = 4, and so it is G state. Since Ms is 0, ∴ S = 0; therefore Spin

1
degeneracy = 2S + 1 = 2 x 0 + 1 = 1 ; Therefore it Singlet G-State ( G)

ML 3 2 1 0 -1 -2 -3

Ms 1 1 1 1 1 1 1

Since ML= 3 ∴ L=3, and Ms = 1 ∴ It will give us Triplet-F term ( 3F)

ML 2 1 0 -1 -2

Ms 0 0 0 0 0

Since ML= 2 ∴ L=2,

and since Ms = 0 ∴ S = 0
∴ It will give us singlet-D term ( 1D)

ML 1 0 -1

Ms 1 1 1

Since ML= 1 ∴ L=1,

and since Ms = 1 ∴ S = 1
∴ It will give us triplet P term ( 3P)

ML 0

Ms 0

Since ML = 0 ∴ L=0, ∴ It will give us S term

and Since Ms = 0 ∴ S= 0 ∴ It will give us singlet S term (1S)

Ground and excited

state terms for d2 configuration

3
F , 3P, 1G, 1D, 1S.

b) How the ground state term of Ni2+ will further due to S-L coupling.

Ground state term is 3F

L=3, and Ms = 1

S-L coupling will give

L+S = 3 +1 = 4

L+S-1 = 3+1-1= 3

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

L+S-3 = 3+1 – 3 = 1

L+S-4 = 3+1-4 = 0

So gives rise to the following terms: 3F4, 3F3, 3F2, 3F1

c) Show splitting of 3P term in octahedral field. (2)

d) Evaluate total degeneracy of 1G state. (2)

(2S+1)(2L+1)

= (2(0)+1)(2(4)+1)

= 1(9)

=9
Q-2 a. Show that Configuration (t2g)2 is equivalent to configuration (t2g)5(eg)2 in
octahedral field? (2)

(t2g)5(eg)2 = (t2g)2

(t2g)5(eg)2 = (t2g)3 (t2g)2(eg) 2

(t2g)5(eg)2 = (A) (t2g)2(A)

(t2g)5(eg)2 = (t2g)2

b. Why Configuration (eg)1 is considered equivalent to (t2g)3(eg)3 in octahedral field?

(eg)1 = (t2g)3(eg)3

(t2g)3(eg)3 = (t2g) ⊕3(eg)2⊕ (eg)1

(t2g)3(eg)3 = A⊕ A ⊕ (eg)1

(t2g)3(eg)3 = (eg)1

c. Why only one high intensity absorption peak is observed in Ti 3+ while more than one peaks are
observed in Ti2+case? (4)
Ti3+ is a d1 system while Ti2+ is a d2 system. D1 system gives one absorption peak in the spectrum while
d2 system gives more than one peak. Their electronic configuration is as follows:

Ti²⁺ = 1s² 2s² 2p⁶ 3s² 3p⁶ 3d²

Ti³⁺ = 1s² 2s² 2p⁶ 3s² 3p⁶ 3d¹

D2 system spectra

D1 system spectra


d. Jahn teller splitting ( ) in d9 system is much greater than in d6; why? (4)
There’s greater splitting in d9 system since the electrons undergoing distortion are present in the higher
energy orbital set eg2. On the other hand, the d6 H.S. has electrons present in the t2g which undergo
distortion. Since the ligand approaches head-on in the d9 system, there is greater repulsion d9
experiences than the H.S. d6. Hence, the H.S. d6 experiences much lesser Jahn Teller splitting than d9
system.
Q-3 Write short answer:
a. Make fully labeled correlation diagram for d1-system complexes. (4)

a) Spherically perturbed free ion spectroscopic term,

b) Group theoretical terms in a weak octahedral field.

c) Group theoretical terms in a strong octahedral field.

d) Electronic configuration in a strong octahedral field.

b. Show that configuration ((eg)1 is equivalent to (t2g)3(eg)3 in the octahedral field. (4)

(eg)1 = (t2g)3(eg)3

(t2g)3(eg)3 = (t2g) ⊕3(eg)2⊕ (eg)1

(t2g)3(eg)3 = A⊕ A ⊕ (eg)1

(t2g)3(eg)3 = (eg)1

c. Ground State of (t2g)2 configuration gives rise to following terms:

(t2g)2 = 1A1g + 1Eg + 1T2g + 3T1g . Show that total # of microstates on the two sides are equal.

(t2g)2 = 1
A1g +
1
Eg +
1
T2g +
3
T1g
6/1x5/2 = 1x1 + 1x2 +1x3 +3x3

15 = 1 +2+3+9

15=15
Q-4 Character table for D4 point group is shown below. Reduce the given reducible representation
Γ1 (in red) and find # of A1 and E representations in it. (10)

D4 E 2C4(z) C2 2C’2 2C’’2 Linear & rotation Quadratic functions

fuctions functions

A1 1 1 1 1 1 X2 + Y2, Z2

A2 1 1 1 -1 -1 Z, Rz

B1 1 -1 1 1 -1 X2- Y2

B2 1 -1 1 -1 1 XY

E 1 0 -2 0 0 (X, Y), (RX, RY) (XZ,YZ)

Γ1 4 0 4 0 0

# of A1

=1/8 [(4x1x1)+(0x1x2)+(4x1x1)+(0x1x2)+(0x1x2)

=1/8 [4+0+4+0+0]

=1/8x8

=1

# of E

=1/8 [(4x1x1)+(0x0x2)+(4x-2x1)+(0x0x2)+(0x0x2)

=1/8 [4+0-8+0+0]

=1/8x 4+(-8)

=-1/2
Q-5 What is Jahn-Teller (J. T) theorem? Show which orbital will be stabilized
(go down in energy) and which will be destabilized (go up in energy) due
to J-T effect in the following cases? Preferably make crystal field
diagram for each case to explain your answer. (12)
The Jahn-Teller theorem states that a molecule with a degenerate electronic ground state (orbitals with
the same energy) will distort its geometry to lower its overall energy. This distortion removes the
degeneracy and stabilizes the electronic configuration.

a. (t2g)3(eg)1

b. (t2g) 3(eg) 3
c. (t2g)5(eg)4