RYSTAL FIELD THEORY (CFT Sallent featuhe 2011

The crystal field theory was developed by H. Bethe and V. Bleck. This theory is based on
entirely different assumptions than the valence bond theory (VBT). As we have already learmt, the
oalence bond theory considers the bonding between the metal ion and the ligands as purely ovalent. On the
other hand, thecrystalfield theory considers the bond between metalion andtheligand as purelyelectrostatic.
This theory is based on the assumption that the metal ion and the ligands act as point charges and
the interactions between them are purely electrostatic. In case of negative ligands (anions such as
C , Br, CN), the interactions with metal ions are ion - ion interactions. If the ligands are neutral

molecules (such as NH,H0,CO), the interactionswith themetal ion areion-dipoleinteractions For

example, in the case of complex ion [CoFthe interactions are between Co andF ions whereas
in [Co(NH)P", the interactions are between negatively charged end of NH, molecule (&-charge on
Natom) and Co* ion.
The central idea of this theory is that the electrons ofthe metalion in the environment of other
ionsormolecules (ligands), as for example, within thelatticeof a crystal areaffected by the non-
sphericalelectricfhield establishedby thesurroundingions ormolecules.Theelectricfieldwascalled
the crystalinefeld,butnow,itiscalled ascrysialfield.Thisisresponssiblefprtheramecrystalfieldtheory.
X Basis of Crystal Field Theory
The basic assumptions of crystal field theory are

( Thetransition metalionissurrounded by theligands with lonepairs ofelectrons.

(i) All types of ligands are regarded as point charges. The ligands may be either ionic
(F, C, CN , etc.) or molecules (such as H,O, NH, CO, etc.). If the ligand is a neutral molecule, then
 MODERN APPROACH TO INORGANIC CHEMISTRY (B.Sc. I)
14
the negative end of the dipole is oriented towards the metal ion. For example, ammonia, NH, is polar
molecule having &-negative charge on N and 8+ charges on H atoms. Similarly, water is also polar
and 8+ charges on H atoms.
with &-charge on O
H H
N H
b+
H H
Ammonia Water

(n) The interactions between the metal ion and the negative ends of anion (or
ion dipoles) is purely electrostatic, i.e. the bond between the metal and ligand is
considered 100% ionic.

(iv) The ligands surrounding the metal ion produce electrical field and this electrical field
influences the energies of the orbitals of central metal ion, particularly d-orbitals.
()In the caseoffree metalion, allthefived-orbitalshavethesameenergy.These orbitals having
the same energies are called degenerate orbitals. This means thát an electron can occupy any one of
these five d-orbitals with equal ease. Howeve, on the approach of the ligands, the orbital electrons
will be repelled by the lone pairs of the ligands. The repulsion will raise the energy of the d-orbitals.
Ifall the ligands approaching the central metal ion are at equal distance from each of the d-orbitals,
the energy of each orbital will increase by the same amount. Therefore, these orbitals will still remain
degenerate, but they will have higher energythan befpre. But we know that d-orbitalshavedifferent
orientationsand, therefore,theseorbitals experience differentinteractions from the ligands. The
will
orbitals lying in the direction oftheligands,willexperiencegreaterrepulsionand theirenergieswill
be raised to greater extent. On the other hand, the orbitalslying away from the
approach of the

igands wil have lesser interactions and therefore their energies will be raised tolesser extent
Therefore, due to the electrical field of the ligands, the energies of the five d-orbitals will split up. This
ogversionoffive degenerate d-orbitals ofthe metalion into different sets oforbitalshavingdisterent
energies in the presence of electricalfieldof ligands is called crystal field splitting. This concept
forms the basis of crystal field theory.
(oi) The number of ligands (coordination number) and their arrangement (geometry) around
the central metal ion will have different effect on the relative energies of the five
d-orbitals. In other words, the crystal field splitting will be different in different structures with
different coordinationnumbers.
(Di) The magnetic properties, spectra and preference for particular geometry can be explained
in terms of splitting of d-orbitals in different crystal fields.
Thus, to understand the crystal field theory, it is essential to have a clear picture of the
disposition of the five d-orbitals in space and the geometrical arrangement of the ligands around the
central metal ion. We may illustrate this concept by considering the compleses with coordination
number 6 and 4, which are very common.
Shapes of d-orbitals

There
arefived-orbitals. These are designated asd d22 and d,2.The shapes ofthese
orbitals are described below:
() The three orbitals dy dyz and d,x are similar and each consists of four lobes of high electron
 Crystal Field Splitting in Octahedial Complexes
In an octahedral complex (cordnation nunber h),
the metal ion is at the centre of the on tahedon and the
ligands the six c o e s as hown in lig. 13. The
are at

three axes X, Y nd 7 point aln, the corner, of tlh

octahedron and are also shown. Iet us suppose that the
metal ion, M"", has a single d-electron (d' configuration,
eg. Ti* in [TiF,T). In the tree1on, when there are o

igands the electron can occupy any one of the five d-

orbitals because all are of the same energy, and are
called degenerate orbitals.

octahedron
Fig. 13.Six ligands at the corners of an
surrounding the metal ion, M"

However, in the octahedral complex MX, all the five d-orbitals will not remain of equal energy
This can be easily understood by considering the shapes of these orbitals. The comparison of

arrangement of d-orbitals
in 14 shows that the two lobes of d,2 orbitals and four lobes of d
Fig.
orbital point directly towards the corners of the octahedron, where the negative charges of the
ligands are concentrated. The remaining three orbitals are oriented in between the axes In the caseot

******.
***
***
*

********

***
***
**.

eorbitals

Orbitals
Fig.14. Orientations of ditlerent d-orbital in an oahedal field of six igands.
 METAL LIGAND BONDING IN TRANSITION METAL COMPLEXEs-
ctahedral complexes, the tome two orbitals are designated as e, (pronounced as "e-g")orbitals
17
whilethe latler three orbitals are designaled as pronouneed as "1-twog") orbitals. Asthe Fwo
ligands approach the central ionalong The aCS, the r, orbilals are repelled more than the t,,orbitals. In other
Nords. 7hr cnergy of the d,2 and d, 0ybitals ime reases muh mmore han the energy of the d d a n d d
rbitals (u should be renmembered that when a charge is repelled by a similar charge,its potentia
hCT Inereases. The greater the rePulsion, the grealer is the increase in energv).
Thus, in octahedral complexes, the five d-orbitals split up into two sets: one set consisting of
Ioorbilals olhigher energy orbitals) and the other set consisting of three orbitals of lower energy
rbilals). The phenomenon of crystal field splitting in an octahedral complex isillustrated in
Fig 15

0.6 A or 6 Dq
o r 10 Dq

3 or 4 Dq

-----
0.4

Energy of òrbitals Splitting of orbitals

in spherical treld in octahedral field
Free ion of ligands state lI stateII

Fig. 15. Crystal field splitting in an octahedral complex.

The
energy difference between twosets ofd-orbitals; t2, and e, is called crystal field splitting
energy and is symbolically represented as A,(The subscript ()standsfor octahedral).The magnitude
of varies for different complexes.The crystal field splitting is also measured in terms of another
parameter called Dq. The two are related as
4 10 Dq
These two parameters are very commonly used.
It may be noted that the crystal field splitting occurs in
of the d-orbitals does not change. This is known as
such a way that the average energy
barycentre
rule which is similar to 'centre of
gravuty type rule. This nreans that the decrease in energy of the set of orbitals that lie at the lower
energy level must be balanced by the
corresponding increase in other set. Theretore, in terms of total
energy 10 Dq, the energy of each of the twoe, orbitals is raised
by 6 Dq and the energy of each of the
threet, orbitals is lowered by 4 Dq. In lerms of A, the energy of each of the twoe, orbitals is raised
by 3/5 A (or 0.6 A) and the energy of each of the three t,, orbitals is lowered
The value of 10 Dq or is by 2/5 A, (or 0.4 A).
, measured speclrocopis.ally.
In Fig. 15, we observe
energies of all the five d-orbitals are raised equally as shownin state that initially the
ield created by the II. This would be observed if the
into two sets
ligands were
spherically symmetrical. however, the energies of d-orbitals split
because of the diflerent orientation of the
in state l orbitals towards the ligands as shown
 18 MODERN APPROACH TO INORGANIC CHEMISTRY (B.Sc. )
Crystal Field Stabilization Energy (CFSE)
We have learnt that in an octahédral field, the energies of five d-orbitals split-up. Three orbitals
are lowered in energy (,.) and two orbitals are raised in energy (e). We know that electronsalways
preter to occupy an orbital of lower energy. For example,inthe case of d' system (eg. Ti" in [TiF
and is,
the d-electron will preter to occupy a
t,orbital therefore, stabilized byanamount equal to0.4
4,or 4 Dy. The amount by splitting of the d-orbitals into
of stabilization provided IS called
two levels
crystal field stabilization energy. It is abbreviated as CFSE. Thus, in octahedral field for each electron
entering into the f, orbital, the crystal field stabilization is 4 Dq and for each electron entering into
the r, crystal field destabilization energy is +6 Dq Thus, the CFSE is calculated a s the
orbital the
algebraic sum of 4Dqper electron in
t, level and +6 Dq for each electron in , orbital.
CFSE for various Octahedral Complexes
For a d' system (eg.Ti ion) electron will be present in any one of the three orbitals. The
electront configuration may be written as t ' . The crystal field stabilization energy is - 4Dq:

CFSE 1(-4Dq) -4Dq=

(i) For a d system (eg. V3* ion) the electronswill occupy t orbitals with their spins parallel in
accordance with Hund's rule. The electronic configuration is t2 and crystal field stabilization
energy is -8Dq:

Q CFSE 2(-4Dq) = - 8Dq

(ii) Similarly, for a d system (e.g. Cr*), the electronic configuration is t The crystal field
stabilization energy is -12 Dg:

CFSE =3(-4Dq) = -

12Dq

(iu) For a d'system (eg. Mn* ion), there are two possibilities
(4) All the four electrons may occupy t2, orbitals with one electron gets paired. The
electronic configuration may be written as
te'
(b) Three electrons occupy t2, orbitals and the fourthelectron
The configuration may be written goes to one ot thee, orbitals.
as
,'
The actual configuration may be decided on
(nergy required to pair the electrons with one another
the basis of A and the pairing energy (P), i.e. the
The configuration (a) is possible if
A>P. These complexes are called strong field complexes
hecause A is large. In this case, the
complex has less number of
unpaired electrons and
is called low
HTRTOmplex. The configuration (b) is possible AP. if Jt is alled weak field and the
re weak field complexes. In that case, the maximum nunber of electrons remaincomplexes
unpaired
METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES
L
and the complex is called high spin compléx.

Ao Lowspin Aoighspin
complex complex

DDO! Strong ficld

(A>P) oP
Thus, we may generalize that if
AP (strong field) Low spin complex
4P(weakfield) High spin complex
As shown above, for a low spin complex having t20 configuration,
CFSE 4(-4 Dg) =
-16 Dq
However, if we take into account pairing energy (P) also, the net CFSE becomes

Net CFSE =-16 Dq+P

On the other hand, for a high spin complex, having the configuration t2 e
CFSE 3(-4 Da) + 1(6 Dq) = - 6 Dq.

() Similarly, for a d system (e.g. Fe3 ion), there are two possibilities
(a)configuration
Allthefiveelectrons may occupy t2 orbitals
may be written as
with two orbitals get paired. Theelectronic
This is possible if A,>P and the complex will be
called strong field or low spin complex._
(b) The three electrons occupy t2 orbitals and two electrons occupy e, orbitals. The
electronicconfiguration may
be written as t2,e This will be possible if A<Pand the
complex is called weak field or high spin complex.
The CFSE in these two types of complexes will be:
(a) Strong field :A, >P

CFSE =
5(-4Dq) + 2P
-20 Dq +2P

(b) Weak field: 4, < P

CFSE 34Dq) +2(6Dq)

=0
 20 MODERN APPROACH TO INORGANIC CHEMISTRY
(B.Sc. I)
Similarly, d* and d systems have two possibilities depcnding
cry'stal tield splitting energy (A.) and the upon the relative magnitudes of
pairing energy of the electrons (P) The d f' and f"systems
have only one possible oonfiguration.
The CFSE for metal ions having different number of d electrons (d' to d) are given in Table 3.
Crystal Field Splitting in Tetrahedral Complexes 15
The co-ordination number for tetrahedral complexes is 4. The tetrahedral arrangement of four
igands surrounding a metal ion may be visualized by placing ligands on the four of the eight corners
of the cube. The directions X, Y and Z point to the centre of the faces of the cube. From ig. 16, it is
clear that the orbitals d d and d, point between X, Y and -axis (i.e. towards the cen tre ot the

Fig. 16. Tetrahedral field of four ligands around the central metal ion

edges of the cube) whereas the orbitals d and depointalong X, Y and Zaxis t e. to the centres ot
thefaces). It is clear that in tetrahedral held, none of thed-orbitals pointexnactlu to nd th
nd
therefore, the splitting of energy will be less than that in octalhedral field. The three d-orbitals
while the w orbitals
d, are pointing close to the direction in which the ligands are approaching l l
Therefore, the energies of the three
orbita e

a and d2 are lying in between the ligands.

raised while theenergies ofthe twoorbitalswill be lowered. Thus, in the presence of tetrahedral field
the degeneracy of five d-orbitals split-up as:

and d2 become stable and their energies are lowered. These are
(i) The two orbitals, d22
designated as 'e' orbitals.
raised lhese are
() The three orbitals d, d, and d., become unstable and thei energies are

designated as t,' orbitals.

in tetrahednal field, the subscripl ' is not

It may benoted that for the splitting of d-orbit.als
used. For example,the orbitalsd and d" are esagnateed s o i t a b w hereas the other three

orbitals d, d
and d,, are designated as . Thr. beearse a tetrahedral geometry has no centre
of symmetry The symbols and ' v e eaing niy tor nehds which have centre of

symmetry.
 METAL LIGAND
BONDING IN TRANSITION METAL COMPLEXES
ale y s t a l field stabilization energies f o r m e t a l ions having different n u m b e r s or

d-electrons in octahedral complexes.

Number of Weak field CFSE Strong field CFSE
d electrons

4Dq
or

0.4

8Dq
or
- 0.8A,

- 12Dq

or

1.24

- 6Dq - 16Dq-P
or or
- 0.6
-

1.6 A +P
d
-20Dq-2P
XLX)
or

(1tX - 2.0 A2P

4Dq
or -24Dg2P aieor
- 0.4,

d 8Dq
or
t - 18Dq +P

- 0.80, or
-

L.S A P
- 12Dq
d
- 1.2A
Or 12D
1.2

d 1T) 6Dq
Or

141411) 0.6

(14Y 14 0
d
(111)
lh v
,
n d h i v e .net Onligurath
Ontigiratimin i t l k et w e k teitt
il,t
Thesvstems d', d strng tield and, thTefore, have
Same CFSE values
 0-4454,
22
MODERN APPROACH TO INORGANIC CHEMISTRY (B.Sc. I)

This is diagrammatically shown in Fig. 17.

1DZ
CO0o0 ,or 10 Dq

Y2.04Dz
Free ion
Energy of d orbitals Splitting of orbitals
spherical field of ligands in tetrahedral field

field splitting in a tetrahedral field.

Fig. 17. Crystal
The magnitude of crystal field splitting is the difference between e andt, orbitals and is
designatedas a, (the subseriptt indicating tetrahedral complexes). It isalsomeasured interms of Dq
and
A =10 Dq
If we compare the magnitude of crystal field splitting in octahedral and tetrahedral complexes
(having same metal ion, ligands and metal ion-ligand distances), it has been observed that the crystal
field splittingintetrahedralcomplexes (4,) is considerablyless thanin octahedral complexes (4). It
hasbeen tound to be

2o13,1
easons for the smaller value of crystal field splitting in tetrahedral than in octahedral
romplexes
There are two main reasons for this
() Intetrahedral complexes there are four ligands while there are six ligands in octahedral
complexes. Therefore, lesser ligands produce less crystal fieldsplitting. The crystal field
splitting in tetrahedral field is about two third of the octahedral field.
(ii) In tetrahedral field, none of the orbitals is
pointing directly
splitting is less.du TopUUbm 18 es. towards ligands
the and, therefore,
Since the magnitude of
crystal field splitting in
pairing energy, therefore, the pairing of electronstetrahedral field is quite small and is always less than the
will never be energetically favourable. Thus, all the
tetrahedral complexes are high spin complexès. No tetrahedral complex with low spin
found to exist. has been
CFSE for Tetrahedral Complexes
As we know that an electron
always prefer to occupy an orbital of lower energy. Since
energy the d-orbitals does not.change
of average
(barycentre rule), theretore, in terms of 10 Dq the energy
each of the e orbital is lowered by 6
Dq and the energy of each of the t, orbital is raised of
is therefore, calculated as by 4 Dq. CFSE
the algebraic sumof-6Dqperelectron ine orbital and+4Dqfor
each
in t, orbital. In terms of A, the electron
energy of eache orbital is lowered by 3/5A, (or 0.6 while each of the
t, orbital is raised by 2/54,(or 0.4 A). A,)
For example,
(i) For d' system, the electronic configuration is c'. Therefore,
 METAL LIGAND BONDING IN
TRANSITION METAL COMPLEXES 23
CFSE 1(-6 Da) = - 6 Dq

Q.
(i) For d system, the electronic configuration is e. Therefore,

CFSE 2(-6 Dg) = -12 Dq

11 Forg system, the electronic configuration is e?t'. As already discussed, crystal field splitting
intetrahedralfield isquitesmalland is alwayslessthanthepairingenergy. Therefore, pairng aoes
not occur and most of the cemplexes are high spin complexes. Therefore,

CFSE=2-6 Dq) + 1(4Dq) = - 8Dq

for complexes with metal ions different configurations of d-orbitals án

The CFSE having
tetrahedral field are given in Table 4.
for tetrahedral complexes with metal ions having different
Table 4. Crystal field stabilization energies
numbers of d-orbitals.

crSE-6D
CFSE-6Dq 2 CFSE -
12Dq

OO - - - - - - - -

CFSE-8Dq CFSE- 4Dq

CFSE = 0
45 CFSE=-6Dq
210
- -

X)
-

CFSE=-12Dq CFSE- 8Dq

_
d
X1) CFSE=- 4Dq d10 CFSE =0

energies are not given.

For simplicity, the pairing