MODULE THREE

CRYSTAL FIELD THEORY (CFT)

 Unit One – The theory

 Unit Two – Spectrochemical series and magnetic properties
 Unit Three – Jahn-Teller Distortion and Square Planar complexes
 UNIT Four – Crystal Field Stabilization Energy (CFSE)

UNIT ONE – The Theory

This theory explains the bonding between metals and ligands to be electrostatic where
the metal is positively charged and the ligands are negative spherical point charge.
Before the ligands approach the metal the d-orbitals are degenerate (i.e. equal in energy).
Although the electrons of the ligands are attracted to the metal ion because it is
positively charged but as the ligands approach closer to the metal ion there is also
repulsion between the electrons in d-orbitals and ligands. This effect raises the energy
of the d-orbital and consequently split them. The direction of approach of the ligand
to the d-orbitals affect the type of splitting that occurs.

Considering the d-orbitals on the x-, y-, z- axis; the 𝑑𝑥 2−𝑦2 is pointing along the x- and
y-axis and the 𝑑𝑧 2 points along the z-axis. While the 𝑑𝑥𝑦 lies between the x- and y-axis;
𝑑𝑦𝑧 lies between the y- and z-axis and 𝑑𝑥𝑧 lies between the x- and z-axis.

 If the ligands are approaching directly along the x, y, z axis, then they affect the
𝑑𝑥 2−𝑦2 and 𝑑𝑧 2 and then raise their energy while the 𝑑𝑥𝑦 , 𝑑𝑦𝑧 and 𝑑𝑥𝑧 are
lowered in energy.
 If the ligands are approaching in between the x, y, z axis, then they affect the
𝑑𝑥𝑦 , 𝑑𝑦𝑧 and 𝑑𝑥𝑧 directly raising their energy while that of the 𝑑𝑥 2−𝑦2 and 𝑑𝑧 2
are lowered.
Crystal field is the field created by the electrostatic interaction as the point charges are
arranged in an orderly manner (like crystal structure). The difference in energy between
the higher and lower energy level of the crystal field splitting is given by ∆.
In an octahedral environment the d-orbital are split as illustrated in the diagram below.
The 𝑑𝑥𝑦 , 𝑑𝑦𝑧 and 𝑑𝑥𝑧 are lowered in energy hence are stabilized and possess a t2g
symmetry while the 𝑑𝑥 2−𝑦2 and 𝑑𝑧 2 are higher in energy are destabilized and possess eg
symmetry. Therefore the energy difference between the t2g – orbitals and the eg –
orbitals is labelled as ∆𝑜𝑐𝑡 which is the crystal field splitting parameter in an octahedral
field. The orbital in the eg set are raised by 0.6∆𝑜𝑐𝑡 (⅗∆oct ) with respect to the
barycentre while those of the t2g set are lowered by −0.4∆𝑜𝑐𝑡 ( -⅖ ∆oct ).

dx2-y2 dz2
eg
0.6Doct
Energy

Doct barycentre
-0.4Doct
t
dxy dyz dxz 2g
Splitting pattern in an octahedral field

In a tetrahedral environment the ligands approach the 𝑑𝑥𝑦 , 𝑑𝑦𝑧 and 𝑑𝑥𝑧 directly and
this result in a splitting which is the inverted form of the octahedral complex. So the
𝑑𝑥𝑦 , 𝑑𝑦𝑧 and 𝑑𝑥𝑧 are raised and the 𝑑𝑥 2−𝑦2 and 𝑑𝑧 2 lowered. Because this is a
tetrahedral complex, the 𝑑𝑥 2−𝑦2 and 𝑑𝑧 2 are now labelled e and the 𝑑𝑥𝑦 , 𝑑𝑦𝑧 and 𝑑𝑥𝑧
are labelled t2. The t2 orbitals are raised by 0.4∆𝑡𝑒𝑡 (⅖∆tet) and e orbitals are lowered by
−0.6∆𝑜𝑐𝑡 (-⅗∆tet ) with respect to the barycentre. However the ∆tet is less than ∆oct
𝟒
i.e. ∆𝐭𝐞𝐭 = ∆𝐨𝐜𝐭 .
𝟗

dxy dyz dxz t2

0.4Dtet
Energy

Dtet barycentre
-0.6Dtet

dx2-y2 dz2
e
Splitting pattern in an tetrahedral field
UNIT TWO – Spectrochemical series and magnetic properties
The magnitude (size) of ∆ depends on the strength of the ligands. Ligands that result
in large values of ∆ are referred to as strong field ligands and those that result in small
values of ∆ are called weak field ligands. The arrangement of ligands according to their
field strength is called the spectrochemical series. Strong field ligands force the electrons
in the d-orbitals to pair up. Electrons fill in singly first before paring, however due to
the wide crystal field splitting caused by strong field ligands, the electrons cannot enter
the raised d- orbitals and would rather pair up in the lowered d-orbitals.
These will force pairing
𝐼 − < 𝐵𝑟 − < 𝐶𝑙 − < 𝑂𝐻 − < 𝑅𝐶𝑂2− < 𝐹 − < 𝐻2 𝑂 < 𝑁𝐶𝑆 < 𝑁𝐻3 < 𝑒𝑛 < 𝑁𝑂2 < 𝑃ℎ𝑒𝑛 < 𝐶𝑁 ≅ 𝐶𝑂
Order of increasing field strength
Note that in some case NH3 can force pairing.

Another factor that affects the crystal field energy is the oxidation state of the metals
ions:
𝐌𝐧(𝐈𝐈) < 𝐍𝐢(𝐈𝐈) < 𝐂𝐨(𝐈𝐈) < 𝐅𝐞(𝐈𝐈𝐈) < 𝐂𝐫(𝐈𝐈𝐈) < 𝐂𝐨(𝐈𝐈𝐈) < 𝐑𝐮(𝐈𝐈𝐈) < 𝐌𝐨(𝐈𝐈𝐈) < 𝐑𝐡(𝐈𝐈𝐈) < 𝐏𝐝(𝐈𝐈) < 𝐈𝐫(𝐈𝐈𝐈) < 𝐏𝐭(𝐈𝐕)
Increasing field strength

(i) Increase in oxidation number: the higher the oxidation number the smaller the
size of the ion but the greater the charge density (charge/volume). As result
shorter metal-ligand distance hence stronger interactions and this increases
the crystal field strength.
(ii) Going down a group shows that the large size of the 4d and 5d orbitals has a
greater impact than the 3d hence stronger interaction and this leads to larger
splitting of these d-orbitals hence large Δ.

An octahedral complex made up of

An octahedral complex made up of
d7 metal ion bonded to a weak field ligand
d7 metal ion bonded to a strong field ligand

When electrons are forced to pair the complex is referred to as being low spin and in
the absence of forced pairing it is described as high spin. Low spin is a state where
there are few paired electrons while high spin state has a higher number of unpaired
electrons. These occur in in d4 to d8 .
UNIT THREE - Jahn-Teller Distortion and Square Planar Complexes
An octahedral complex undergoes distortion in its shape. This distortion can take place
either by the elongation of the axial ligands or the compression of equatorial ligands.
This effect occurs when the ground state electronic configuration is asymmetrically
filled making the geometry unstable and in order to bring about stability the distortion
occurs. A common example is d9 complexes of Cu(II). It can also occur with high spin
d4 and low spin d7. This distortion is called Jahn-Teller Distortion (or tetragonal
distortion).
L

L L
L L L L
L L
M Elongantion of axial ligands M Compression of equotorial ligands M

L L L L L
L
L L
Regular octahedral complex
L Distored complex
Distored complex

dx2-y2

dz2
dx2-y2 dz2
Energy

dxy
dxy dyz dxz
Regular octahedral complex
dyz dxz
Jahn-Teller distortion

The asymetrical filling of the eg orbital caused the distortion

There are no ligands approaching the metal along the z-axis and this greatly stabilize
(lowers) the 𝑑𝑧 2 orbital as well as lower the energy of the 𝑑𝑥𝑧 and 𝑑𝑦𝑧 while the 𝑑𝑥 2−𝑦2
and 𝑑𝑥𝑦 will be raised.

A square planar shape can be derived from the octahedral geometry by removing the
two axial ligands (ligands along the z-axis). This would greatly stabilize the 𝑑𝑧 2 orbital
as well as lower the energy of the 𝑑𝑥𝑧 and 𝑑𝑦𝑧 while the 𝑑𝑥 2−𝑦2 and 𝑑𝑥𝑦 will be raised.
For example, some Cu2+ complexes are square planar instead of the expected
octahedral. This is due to Jahn-Teller distortion, bonding at the equatorial position
readily occurs as the bonds are short. However, the weak interactions at the elongated
axial position result in the ease to lose these ligands, yielding a square planar complex
rather than octahedral.
dx2-y2
L
L
dx2-y2 dz2 Doct
L L L

M remove axial ligands M Doct dxy

L L
L L dxy dyz dxz dz2
Square planar
L Octahedral
complex dyz dxz
Octahedral field
Square planar
complex
. field
UNIT FOUR - Crystal field stabilization energy (CFSE)
CFSE is defined as the energy of the electronic configuration in the ligand field (LF)
(splitting of d orbitals) minus the energy of the electronic configuration in the
isotropic field (IF) (before splitting). This is the decrease in energy resulting from the
crystal field splitting.
𝐂𝐅𝐒𝐄 = 𝐄𝐋𝐅 − 𝐄𝐈𝐅

Energy = (number of electrons n) × (corresponding splitting parameter∆) +

(number of paired electrons m) × (spin pair energy P)
𝐸𝐿𝐹 = (𝑛∆ + 𝑚𝑃)
In an isotropic field both ∆𝐨𝐜𝐭 and ∆𝐭𝐞𝐭 = 0 because there is no splitting
𝐸𝐼𝐹 = (𝑚𝑃)

In an octahedral environment the CFSE d-orbital are as illustrated.

1
For a d1 (𝑡2𝑔 )
𝐸𝐿𝐹 = 1 × (−0.4∆𝑜𝑐𝑡 ) = −0.4∆𝑜𝑐𝑡
𝐸𝐼𝐹 = 0
isotropic field CFSE = ELF − EIF = −𝟎. 𝟒∆𝒐𝒄𝒕
ligand field
2
For a d2 (𝑡2𝑔 )
𝐸𝐿𝐹 = 2 × (−0.4∆𝑜𝑐𝑡 ) = −0.8∆𝑜𝑐𝑡
𝐸𝐼𝐹 = 0
isotropic field CFSE = ELF − EIF = −𝟎. 𝟖∆𝒐𝒄𝒕
ligand field
3
For a d3 (𝑡2𝑔 )
𝐸𝐿𝐹 = 3 × (−0.4∆𝑜𝑐𝑡 ) = −1.2∆𝑜𝑐𝑡
𝐸𝐼𝐹 = 0
isotropic field CFSE = ELF − EIF = −𝟏. 𝟐∆𝒐𝒄𝒕
ligand field
 For a d4, there are two situations
3
(i) No pairing (𝑡2𝑔 , 𝑒𝑔1 )
𝐸𝐿𝐹 = 3 × (−0.4∆𝑜𝑐𝑡 ) + (1 × 0.6∆𝑜𝑐𝑡 ) =
−06∆𝑜𝑐𝑡
isotropic field 𝐸𝐼𝐹 = 0
ligand field CFSE = ELF − EIF = −𝟎. 𝟔∆𝒐𝒄𝒕

4
(ii) Pairing (𝑡2𝑔 , 𝑒𝑔0 )
𝐸𝐿𝐹 = 4 × (−0.4∆𝑜𝑐𝑡 ) + 1𝑝 =
−1.6∆𝑜𝑐𝑡 + 𝑃
isotropic field 𝐸𝐼𝐹 = 0
ligand field CFSE = ELF − EIF = −𝟏. 𝟔∆𝒐𝒄𝒕 + 𝑷

In a case like this the preferred configuration is the one with lower energy. Pairing is
often avoided, however when it does occur the pairing electrons experience strong
repulsion called the pairing energy P. When there are no forced pairing electrons will
fill in singly before pairing (high spin d4 – d8).
If ∆𝑜𝑐𝑡 < 𝑃, then electrons will not pair. This is a weak field.
If ∆𝑜𝑐𝑡 > 𝑃, then electrons will pair. This is a strong field.

Class work
Calculate the crystal field stabilization energy of (i) high spin d7 (ii) low spin d7.

For a high spin d7 (𝒕𝟓𝟐𝒈 , 𝒆𝟐𝒈 )

𝐸𝐿𝐹 = 5 × (−0.4∆𝑜𝑐𝑡 ) + 2𝑃 + (2 × 0.6∆𝑜𝑐𝑡 )
(−2.0∆𝑜𝑐𝑡 ) + 2𝑃 + (1.2∆𝑜𝑐𝑡 )
(−0.8∆𝑜𝑐𝑡 ) + 2𝑃
𝐸𝐼𝐹 = 2 × 𝑃 = 2𝑃
CFSE = ELF − EIF = [(−0.8∆𝑜𝑐𝑡 ) + 2𝑃] − 2𝑃
𝐶𝐹𝑆𝐸 = −0.8∆𝑜𝑐𝑡
For a low spin d7(𝒕𝟔𝟐𝒈 , 𝒆𝟏𝒈 )
𝐸𝐿𝐹 = 6 × (−0.4∆𝑜𝑐𝑡 ) + 3𝑃 + (1 × 0.6∆𝑜𝑐𝑡 )
(−2.4∆𝑜𝑐𝑡 ) + 3𝑃 + (0.6∆𝑜𝑐𝑡 ) = −1.8∆𝑜𝑐𝑡
(−1.8∆𝑜𝑐𝑡 ) + 3𝑃
𝐸𝐼𝐹 = 2 × 𝑃 = 2𝑃
CFSE = ELF − EIF = [(−1.8∆𝑜𝑐𝑡 ) + 3𝑃] − 2𝑃
𝐶𝐹𝑆𝐸 = −1.8∆𝑜𝑐𝑡 + 𝑃

The same is applicable in a tetrahedral environment only this time instead of ∆𝑜𝑐𝑡 ;
∆𝑡𝑒𝑡 would be used. (Remember to reverse the orbitals)