Crystal Field Stabilisation Energies

(CFSEs) of Octahedral Complexes

We have seen that, according to CFT, under the influence of the six ligands approaching
towards the central metal ion during the formation of an octahedral complex, the d-orbitals of
the central metal ion are split into two sets of orbitals viz., lower energy triplet (or trio) t2g,
and higher energy doublet (or pair) eg sets. t2g set of orbitals is triply degenerate while eg set is
doubly degenerate The energy gap between these two sets is equal to ∆0 (or 10Dq). The
energy of t2tg set is lowered by 2/5 ∆0( = 0.4∆0) or 4Dq while that of eg set is raised by 3/5∆0
(= 0.6∆0) or 6Dq relative to the energy of hypothetical degenerate d-orbitals. Thus each
electron occupying t2g orbitals decreases the energy of d-orbitals by —0.4∆0 (= —4Dq) while
that going into eg orbitals increases its energy by + 0.6∆0 (= + 6Dq). - and + signs indicate
respectively the decrease and increase in the energy of d-orbitals caused by their splitting
under the influence of six ligands. Now let us consider a dx ion containing t2gpegq
configuration in which p is the number of electrons in t2g set, q is the number of electrons in
eg set and x = p + q. Quite obviously :

Calculation of energy:-
Change in energy (in terms of∆0 ) for t2gpegq configuration
= Loss in energy due to p electrons in t2g set
+ gain in energy due to q electrons in eg set.
=-0.4 ∆0 x p +0.6∆0 x q
= [-0.4 p + 0.6q] ∆0
……(i)
Now since t = 10 Dq, the above expression can also be written as
Change in energy (in terms of Dq) for t2gpegq configuration
= [-0.4p + 0.6q] x 10 Dq
= [-4p + 6q]Dq
……(ii)
Thus equations (i) and (ii) give the energies of dX ion containing t2gpegq configuration. The
change in energy for dx ion containing t2gpegq configuration calculated as above is called
crystal field stabilisation energy (CFSE) of dx ion, since it stabilises d-orbitals by lowering
their energy which results from their splitting into t2g and eg orbitals.
In the derivation of equations (i) and (ii) we have not considered the pairing energy, P of dX
ion which is the energy required to pair two electrons against electron-electron repulsion in
the same orbital. If the pairing energy of the ion is also involved in any t2gpegq configuration
of a given dx ion, then CFSE of the ion is given by the expression. :
= [- 0.4p + 0.6q] ∆0 x m p
...(iii)
=[-4p+6q]Dq + mp (.. . ∆0= l0Dq)
….(iv)
Here m is the total number of paired electrons in t2g and eg sets of orbitals. Equations (iii) and
(iv) have been used to calculate the CESE values (in terms of∆0 and Dq respectively) for d° to
d'° ions of high spin and low spin octahedral complexes. These values, as calculated from the
above equations, are given below:

(a)For high spin (or spin free or weak field) octahedral complexes:
Do (t02g e°g , p = 0, q = 0) = 0.0∆0 or 0.0 Dq; d1 (t2'g e°g, p = 1, q = 0.) = - 0.4 Ao or - 4Dq;
d2(t22ge0g, p = 2, q = 0) = - 0.8 ∆0 or -8 Dq; d3 t32ge0g, p = 3, q = 0) = - 1.2 ∆0 or -12 Dq; d4
(t32geg1,p = 3, q = 1) = -0.6 ∆0 or -6 Dq; d5 (t3 eg2 ,p = 3, q =2) = 0.0 ∆0 or 0.0Dq ; d6 ( t2g4 eg2 ,p
= 4,q = 2, m = 1)= -0.4∆0 + P or -4Dq + P ; d7 (t52geg2 , p = 5, q = 2, m = 2) = - 0.8 ∆0 + 2P or -
8 Dq + 2P; d8(t 62geg2, p=6, q = 2, m = 3) = - 1.2∆0 + 3P or - 12 Dq + 3P; d9 ( t 62g eg3, p =6,q
=3, m =4)= - 0.6∆0 +4P or - 6Dq + 4P;d'°(t 62geg4 ,p = 6,q = 4, m =5)= 0.0∆0 +5P or O.OD +
5P.

(b)For low spin (or spin paired or strong field) octahedral complexes
D0 (t°2g eg°, p = 0, q = 0) = 0.0∆0 . or 0.0 Dq; d' (t'2geg0 , p = 1, q = 0) = - 0.4∆0 or - 4Dq; d2 (t2g
eg°, p = 2, q = 0) = - 0.8∆0 or - 8 Dq; d3 (t 32g eg°, p = 3, q = 0) = -1.20∆0 or -12Dq ; d4 (t42geg 0 ,
p=4,q=0,m=1)= -1.6∆0 +P or -16 Dq + P; d5(t 52g eg0, P = 5, q =0, m = 2)= 2.0 ∆0+ 2P or -20
Dq + 2P; d6 (t62g eg0 , p = 6, q = 0, m = 3) = - 2.4∆0 + 3P or - 24 Dq + 3P; d7 (t62g eg1, p = 6, q =
1, m = 3) = -1.8∆0 + 3P or - 18 Dq + 3P; d8 (t6 e g 2 , p=6, q = 2, m = 3)= - 1.2∆0 + 3P or-12Dq
+3P;d9 (t62g e g3 ,p = 6,q =3,m =4)= -0.6 ∆0+ 4P or -6 Dq + 4P;d'°(t 62g e g 4 ,p = 6, q = 4, m = 5)
= 0.0 ∆0+5P or3.0 Dq + 5P.
CFSE values as given above show that, (i) When Ao= P, each of d4 , d5 , d6 and d7 ions gives
the same value of CFSE for both spin states. (ii) When ∆0 > P, the CFSE of the low spin state
becomes smaller than that of the high spin state and hence the low spin state becomes the
preferred state of the ion. In this condition (i.e. when∆0 > P), the electrons tend to pair and
hence low spin complexes are obtained (iii) When ∆0< P, the CFSE of the high spin becomes
smaller than the low spin state and hence high spin state becomes the preferred state of the
ion. Under this condition (i.e. when ∆0 < P) the electrons tend to remain unpaired and hence
high spin complexes are obtained. Thus we see that the spin state of an ion in a complex
depends on whether the crystal field splitting (z)is bigger or smaller than the pairing energy
(P).