Crystal Field Theory

CHM-102
Basic Inorganic Chemistry
 Crystal Field Theory

q Crystal field theory: Definition and understanding

q Splitting of d-orbital energy levels for Oh, Td and square planar complexes
q Application of CFT to explain color and magnetism of transition metal
complexes.
 Crystal field theory: Definition and understanding

q This is an electrostatic model of bonding and simply uses the

ligand electrons to create an electron field around the metal
center.
q And according to CFT there are no metal–ligand covalent
interactions.
q Each ligand is treated as a negative point charge and there is
an electrostatic attraction between the metal ion and ligands.
q However, there is also a repulsive interaction between
electrons in the d orbitals and the ligand point charges.
q If the electrostatic field (the crystal field) were spherical, then
the energies of the five d orbitals would be raised
(destabilized) by the same amount.
Size and Shape of the 5 d Orbitals
Size and Shape of the 5 d Orbitals
 Splitting of d-orbitals in Octahedral Field

q The two d orbitals (dx2-y2 and dz2) that are directed along the x, y and z axes are affected more than
the other three d orbitals (dxy, dxz and dyz)
q The two d orbitals (dx2-y2 and dz2) that are directed along the x, y and z axes are affected more than
the other three d orbitals (dxy, dxz and dyz).
Splitting of d-orbitals in Octahedral Field

eg orbitals

Orbitals “on axis”: “energy increases”

t2g orbitals Orbitals “off axis”: “energy decreases”

 Barycentre

q The energy separation between two sets of orbital is called 𝝙Oct (delta oct) or 10 Dq.
q The overall stabilization of t2g orbitals equals the overall destabilization of the eg set.
q Two orbitals in the eg set are raised by 0.6 𝝙Oct and the three orbitals in t2g set are lowered by 0.4
𝝙Oct with respect to the barycenter.
q Barycentre: The barycenter is the average energy of the d-orbitals.
Three orbitals stabilized by 0.4 𝝙Oct = -1.2 𝝙Oct
Energy is conserved
Two orbitals destabilized by 0.6 𝝙Oct = 1.2 𝝙Oct
 Factor affecting 𝝙Oct (delta oct)
1. Nature of metal ion:
Co3+
As an example with six L and same geometry: The 𝝙Oct for Ir3+ will be more.
Rh3+ 𝝙Oct
Reason: For Rh and Ir, f orbitals are filled and hence the Z* is more and hence can Ir3+
interact ligand more strongly.
2. Charge on metal ion: As an example, the complexes of Fe(II) and Fe(III) for a
given ligand, 𝝙Oct increases with increasing oxidation state.
Reason: More charge density more 𝝙Oct because more interaction with the ligands.
3. Nature of ligands (Spectrochemical series): A concept of weak field and strong
field ligands based on experimental data.
Things to remember in general: Weak field to strong filed with the following donor
atoms (O<N<C)
 𝝙Oct (delta oct) origin and calculation

potential energy
 Crystal Field Stabilization Energy: High and Low Spin Oct.
Complexes
q Crystal Field Stabilization Energy (CFSE) is the energy difference for the given electron
configuration in the crystal field compared to the spherical (isotropic) field.
As an example for a d1 system, the configuration t2g1 . With respect to the barycentre, there is
a stabilization energy of - 0.4 𝝙Oct or 𝝙O which is called crystal field stabilization energy (CFSE).
Formula for calculation of CFSE

q Like wise, CFSE for

• d2 system (t2g2 and eg0): 2 x -0.4 𝝙Oct +0 = -0.8 𝝙Oct.
• d3 system (t2g3 and eg0): 3 x -0.4 𝝙Oct +0 = -0.12 𝝙Oct. Low-spin High-spin
• d4 system two arrangements are possible. CFSE = -1.6 𝝙Oct + P CFSE = -0.6 𝝙Oct

q Pairing energy (P): Pairing energy is the energy required to place two electrons in the same orbital.
 Crystal Field Stabilization Energy: High and Low-spin Complexes

q Pairing energy (P): If the crystal field splitting (𝝙Oct or 𝝙O) is small because of weak-bonding ligands, then
the pairing energy will be larger, and the complex will be high-spin.
q d5 system: Two arrangements are possible.

CFSE = 0 CFSE = -2.0 𝝙Oct+2P

 High-spin and low-spin complex ions of Mn2+

potential energy

𝝙Oct 𝝙Oct

CFSE = 0 CFSE = -2.0 𝝙Oct+2P

 Crystal Field Stabilization Energy: High and Low Spin Complexes
q d6 system: Two arrangements are possible; e.g.,
High spin: [Fe(H2O)6]2+, and Low spin: [Co(CN)6]3+

q High Spin System:

potential energy

CFSE = 4x-0.4 𝝙Oct + 2x0.6 𝝙Oct = -0.4 𝝙Oct

# Note that the pairing in t2g orbital is happening because of
the internal configuration of the metal ion.
# It is not because of the ligand and hence no requirement of
pairing energy from the ligand field side.

q Low Spin System:

potential energy

CFSE = 6x-0.4 𝝙Oct + 0x0.6 𝝙Oct = -2.4 𝝙Oct+ 2P.

# Remember that one pairing was already there even in the
weak ligand field.
#The two extra pairing occurred due to the strong ligand
field and hence 2P will be considered as a part of CFSE.
Crystal Field Stabilization Energy: High and Low Spin Complexes
 Identifying Complex Ions as High-spin or Low-spin
Problem: For each of the two octahedral complex ions [Fe(H2O)6]2+ and [Fe(CN)6]4-, draw an orbital splitting
diagram, predict the number of unpaired electrons, and identify the ion as low or high spin and calculate the
CFSE.
Hint: The electron configuration of Fe2+ gives us information that the iron has 6d electrons. Field strength as per
the spectrochemical series.

Answer: Draw the orbital box diagrams, split the d orbitals into eg and t2g. Add the electrons noting that a weak-
field ligand gives the maximum number of unpaired electrons and a high-spin complex and vice-versa.

[Fe(CN)6]4-
[Fe(H2O)6 ]2+
eg
potential energy

eg

t2g
t2g
4 unpaired e-- no unpaired e--
(high spin) (low spin)

CFSE = 4x-0.4 𝝙Oct + 2x0.6 𝝙Oct = -0.4 𝝙Oct CFSE = 6x-0.4 𝝙Oct + 0x0.6 𝝙Oct = -2.4 𝝙Oct+ 2P.
 Problem: Explain why the CFSE for a low-spin d5 configuration contains a 2P term and d6, d7 have 2P and P
term respectively. Also calculate CFSE for each case.

Hint: Check the solved example of d6 in slides number 13.

Answer: Draw the orbital box diagrams, splitting the d orbitals into eg and t2g. Add the electrons noting that a
weak-field ligand gives the maximum number of unpaired electrons and a high-spin complex and vice-
versa.

High-spin (HS) d5 system Low-spin (LS) d5 system

eg
Assume that the LS complex is formed from the HS complex
potential energy

eg through the influence of strong ligand field which induces

pairing of electrons in same orbital. Here we see that the
pairing is occurred in two orbitals and hence two pairing
energies (2P) are involved.
t2g t2g
one unpaired e--
5 unpaired e-- (low spin)
(high spin)
CFSE = 5x-0.4 𝝙Oct + 0x0.6 𝝙Oct = -2.0 𝝙Oct+ 2P.
 High-spin (HS) d6 system Low-spin (LS) d6 system
eg Assume that the LS complex is formed from the HS by
the strong ligand field which induces pairing of

potential energy
electrons in same orbital. Here also we see that the
eg extra pairing is occurred only in two orbitals and
hence two pairing energies (2P) are involved and one
pairing were already there because of the
configuration.
t2g t2g

5 unpaired e-- one unpaired e--

(high spin) (low spin)
CFSE = 6x-0.4 𝝙Oct + 0x0.6 𝝙Oct = -2.4 𝝙Oct+ 2P.

High-spin (HS) d7 system Low-spin (LS) d7 system

eg Assume that the LS complex is formed from the HS by
the strong ligand field which induces pairing of
potential energy

electrons in same orbital. Here also we see that the

eg extra pairing is occurred only in one orbital and hence
one pairing energies (P) are involved and two pairing
were already there because of the configuration.

t2g t2g

5 unpaired e-- one unpaired e--

(high spin) (low spin)
CFSE = 6x-0.4 𝝙Oct + 1x0.6 𝝙Oct = -1.8 𝝙Oct+ P.
 Jahn-Teller distortions
q The Jahn–Teller theorem states that any non-linear molecular system (like Octahedral systems) in a
degenerate electronic state will be unstable and will undergo distortion to form a system of lower
symmetry and lower energy, thereby removing the degeneracy.
q The unequal filling of electrons in t2g and eg set may cause distortion in the complex.
q The distortion is more if electrons are unequally filled in the eg set because these orbitals lies along
the axis as compared to the t2g set.
q E.g., Octahedral complexes of d9 and high spin d4 are often distorted.
eg set is unequally filled. Two arrangements are possible
High spin d4 system 1. If the singly occupied orbital is dz2, there will be a greater electrostatic repulsion
eg associated with the ligands coming from z axis than with the other four coming from x and y
axis, and therefore the complex suffers elongation at z axis.
Reason: Because most of the electron density in this orbital will be concentrated between
the cation and the two ligands on the z axis.
Note# Elongation of the complex is accompanied by the stabilization of each d orbital that
has a z component, while the dxy and dx2-y2 orbitals are destabilized.
t2g
2. If the singly occupied orbital is dx2-y2, there will be a greater electrostatic repulsion
one unpaired e-- associated with the ligands coming from x and y axis than with the other two ligands from z
(low spin) axis, and therefore the complex suffers elongation at x and y axis and contraction at z axis.
Reason: Same as above.
Jahn-Teller distortions
Possibilities of Jahn--Teller distortions
Splitting of d-orbitals in Square Planar Complexes
Splitting of d-orbitals in Tetrahedral Complexes

Tetrahedral
 Splitting of d-orbitals in Tetrahedral Complexes

q The higher energy for t2 set: Ligand approaches metal in between the axis and all three orbitals of t2
are also present in between the axis.
q The lower energy for e set: This set of orbital experiences minimal repulsion as both of them are
present on axis and ligands are approaching in between the axis.
 Octahedral vs Tetrahedral Complexes
CFSE for 𝝙t

q The crystal field splitting (𝝙t) for Td geometry is intrinsically smaller than the octahedral cases.
q Relationship of 𝝙t with 𝝙oct: 𝝙t = 4/9 𝝙oct.
q Tetrahedral splitting is rarely large enough to result in pairing of the electrons. As a result, low-spin
tetrahedral complexes are not common.