Crystal Field Theory

Crystal Field Theory

• Crystal field theory (CFT) was proposed by Hans Bethe in 1929,
modified by van Vleck in 1935

• Assumptions of the model

➢Proposes an electrostatic model (a model that uses ligands to

create an electric field around the metal centre)

1. Bonding between ligand and metal is electrostatic in nature

2. Metal ion is considered as a positive charge

3. Anionic ligands regarded as negative point charge

4. Neutral ligands as point dipoles (+ve and –ve ends) with the
negative end of the dipole attracted to the metal ion 2
5. In the free atom, all the d orbital are degenerate
(same energy)

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• This degeneracy is destroyed by the ligand when a complex
is formed

• This is due to the splitting of d-orbitals under the influence

of the approaching ligand to the metal

• This then result in the orbital's having different energies

• Since the electrons on the central metal are under repulsive

force from the electrons on the ligand;

✓The electrons occupy the d-orbitals furthest away from the

direction of approaching ligands
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The transition ion and its environment
• The energy level of a given p, d or f set for an isolated atom
or atoms in an electric field which is spherically symmetrical
around the atom are treated as equal

• Consider an atom which is coordinated to two other groups

in a linear configuration (ML2)

• If the groups lie in the z-direction, orbitals which point along

the z-axis will lie in the field of these ligands

➢thus will be affected more than orbitals lying in other

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directions
Degeneracy of p- and d-orbital in a z-directed field

Splitting pattern in p and d orbitals

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• If the groups lie in the z-direction, the orbital which point
along the z-axis will;

➢Be affected by the coordinated groups more than orbitals

lying in other directions

➢This effect will lead to the z-directed orbitals on the central

atom to be in a region of higher negative field than non-z
orbitals

➢Hence electrons will avoid entering them

➢Orbitals as pz, dz2, dxz, dyz would be at a higher energy

compared to the other orbitals
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• But in coordination compounds, splitting effects are
negligible for p and f orbitals

• Most d-block T. M complexes are usually surrounded by four

or six ligands giving tetrahedral or octahedral

• So field produced by the ligands is not spherically

symmetrical

✓d-orbitals are not affected by the ligand field

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Octahedral Crystal Field

❖Metal is at the centre (positively charged)

❖Ligands are the positive (x, y, z,) and negative (x’, y’ z’) ends

of the three coordinates axes (neutral ligand) 9

• There’s an electrostatic attraction between the metal ion
and the ligand

• If the electrostatic field is spherical;

✓Then the energies of the five d-orbitals would be

destabilized by different amount of energies because they
do not have the same orientation in space

✓Orientation of the five d-orbital in an octahedral field shows

that;

➢The lobes dxy, dxz, dyz which point in between the

cartesian coordinates are in between the ligands
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Orientation of the five d orbitals in an octahedral complex

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➢Lobes of dz2 and dx2-y2 orbitals which point along the
Cartesian coordinates also point at the ligands

➢Hence these orbitals are destabilized than dxy, dxz, dyz

orbitals

• Due to orientation of d orbitals, there’s loss of degeneracy

of the orbitals;

✓ dz2 and dx2-y2 being destabilized with respect to the

original d orbital

✓dxy, dxz, dyz orbitals are stabilized with respect to the

spherical field of the d-orbitals in the free metal
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✓This gives rise to a set of two degenarate orbitals;

✓dxy, dxz, dyz (t2g) – three lower degenarate orbital

✓dz2 and dx2-y2(eg) – two higher degenerate orbital

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Splitting of d orbitals in an octahedral complex

✓Δo is octahedral splitting energy (energy difference between

the two sets)
✓Δoct=10Dq 14
Splitting of d orbitals in an octahedral complex showing the
energy change with respect to the barycentre

❑Mean of the energies of the two sets of orbitals is taken as zero (barycentre)
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• In octahedral field, the eg orbitals are destabilized by +3/5 Δo
or +0.6 Δo

• t2g are stabilized by -2/5 Δo or -0.4 Δo

• The magnitude of Δo is determined by the strength of the

crystal field

➢The weak field and the strong field

➢Δo weak < Δo strong

➢The size of splitting energy is measured spectroscopically

by measuring the energy of electronic transition between t2g
and eg orbitals 16
Factors Affecting the Magnitude of the Splitting Energy

• In an octahedral field, crystal field splitting energy Δo

depends on three main factors;

➢The nature of the ligands

➢The charge on the metal or oxidation state of metal

➢Position of the metal (if it is a first row, second or third row

T.M) Δo3d< Δo4d< Δo5d

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The Nature of Ligand
• The size of splitting energy Δo for different ligands was
determined spectroscopically (examination of spectra of series of
complexes

• The order was constant from one ion to the next and increases in
the order;
• I-<Br-<S2--<Cl-<SCN-<NO3-<F-<OH<H2O<oxalate<EDTA<NH3<en<NO2-<CN-<CO
Ligands increasing value of Δo
✓The series is termed spectrochemical series

✓This order is experimentally derived from electronic spectra of

complexes 18
➢The ligands lower in series have a low value of Δo and are
called weak field lignds

➢Ligands higher up with large Δo values have large splitting

and are called strong field ligands

➢Examples of some octahedral chromium (III) complexes

Complex: [CrCl6]3-<[Cr(H2O)6]3+<Cr(NH3)6]3+ <Cr(CN)6]3-

Δo (cm-1): 13,200 17,400 21,500 26,600

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Oxidation State of Metal
• Magnitude of octahedral splitting energy varies with the
oxidation state of the metal

• Octahedral splitting energy increases with O.S of the metal ion

✓Reason; higher oxidation state polarizes the ligands more than

the lower O.S

✓This results in closer interaction between the metal and ligands

✓Hence larger splitting of the d-orbitals

Example
(Δo) for [Co(NH3)6]2+ is 10,100 cm-1 while that for [Co(NH3)6]3+ is
22,900 cm-1 20
Position of Metal
• The splitting energy increase in the order 3d<4d<5d for
metals in a particular group with the same coordination
number

• Complex: [Co(NH3)6]3+ [Rh((NH3)6] 3+ [Ir(NH3)6] 3+

• Δo (cm-1): 22,900 34,100 41,000

• The elements are in the same group but different periods

• When complexed to the same ligand, the order is Co<Rh<Ir

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Use of CFT to explain color of complexes
• Crystal field theory provides explanation for the observed color
in complexes

• Substances which exhibit color absorb certain electromagnetic

radiations from the white light falling on them (radiations in the
range 720-400 nm)

• Since complexes have metal ions with incomplete d-sub shell,

there could be promotion of electrons from lower energy t2g to
higher energy level eg for octahedral complex and from lower
energy level e to higher t2 level in tetrahedral complex
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• So the energy required for such promotion will vary according to
the ligand so that the color of a complex is dependent on the
ligand it contains (weak field or strong field)

• Ligand determines the splitting energy which then determine the

wavelength of absorption

• When a compound has absorption band in the region (720-400

nm) a particular color is absorbed while the compounds shows
the complementary or transmitted color

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➢[Ti(OH2)6]3+ absorbs green and yellow radiations while the
complementary color purple is transmitted
Question
Determine the crystal field splitting energy for Ti3+ in an octahedral field using the
complex ion [Ti(OH2)6]3+

Ti[Ar]4s2 3d2, Ti3+[Ar]3d1

• The single d electron naturally enters t2g1 configuration

• Electron transition from t2g1 to eg1 give rise to single absorption band in the visible
region at a frequency of 20,300 cm-1

• If 1 kj = 83.7 cm-1
• Δox = 20,300 cm-1
• Δo = 20,300 cm-1
• 83.7 cm-1 =243 kj/mol
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• If Cl- ligand is substituted for water
• [TiCl6]3-, absorption at 13,000 cm-1

• t2g1 eg1 13,000 cm-1

• If 1 kj = 83.7 cm-1
• Δox = 13,000 cm-1
• Δo = 13,000 cm-1
• 83.7 cm-1 =155 kj/mol

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