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CFT For LE-1

Crystal field theory (CFT) describes the splitting of d-orbital energies when a central metal ion is surrounded by ligands. According to CFT, ligands are modeled as point charges or dipoles that create an electrostatic field, splitting the d-orbital energies into two sets. For octahedral complexes, the d-orbitals split into the lower-energy t2g set and higher-energy eg set. The magnitude of the splitting (Δ) depends on factors like the metal ion, ligands, and their geometry. CFT successfully explains many properties of transition metal complexes but has limitations as it does not consider covalency in metal-ligand bonding.

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100 views55 pages

CFT For LE-1

Crystal field theory (CFT) describes the splitting of d-orbital energies when a central metal ion is surrounded by ligands. According to CFT, ligands are modeled as point charges or dipoles that create an electrostatic field, splitting the d-orbital energies into two sets. For octahedral complexes, the d-orbitals split into the lower-energy t2g set and higher-energy eg set. The magnitude of the splitting (Δ) depends on factors like the metal ion, ligands, and their geometry. CFT successfully explains many properties of transition metal complexes but has limitations as it does not consider covalency in metal-ligand bonding.

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Rupok
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Crystal Field Theory(CFT)

Brethe and Van Vlick


For the metal-ligand bonding in
the complex compounds
POSTULATES OF CFT
1. According to the CFT, central metal ion (CMI) of the
complexes being surrounded by the number of ligands.
2. According to this theory, ligands can be of the two types
which are given below:
a. Negative ligands also known as point charge.
b. Neutral ligands also known as point dipole.
3. According to CFT there does not occur any type of the
overlapping between the orbitals of the ligand and CMI i.e.
metal ligand bonding having zero % covalenat
1 02/07/2024
Crystal Field Theory(CFT)

4. According to CFT always there occur an electro static


interaction between the +ve charge nucleus of the CMI and –
ve charge of the ligand i.e. metal- ligand bonding having
100% ionic character.

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Crystal field splitting of d-orbital

1. CFT FOR THE OCTAHEDRAL COMPLEXES

Step I- Shape of 5- d orbital’s of CMI:


Five d- orbitals of the CMI can be divided into two
different set of orbital’s which are given below:-

a. t2g set (Non-axial set of d-orbital):


dxy dyz & dzx orbital’s are known as t2g set of orbital’s. All
these orbital being present between the axis due to which
they are also known as Non-axial set of d- orbitals

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Crystal field splitting of d-orbital

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Crystal field splitting of d-orbital

Step II- Orientation of 6 ligands around the CMI in the


octahedral complexes

In the octahedral complexes all the six ligands being


oriented toward the CMI from the six opposite corners
of the three axis, which can be represented:-

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Crystal field splitting of d-orbital
Step III- Crystal field splitting of the 5-d orbital’s of CMI:

Step IV-Distribution of dn configuration


6 of the CMI in the splitted
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set of d-orbitals:
CFE for octahedral complexes

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Calculation of CFSE
Calculation of CFSE

∆0 < P ∆0 > P

Hund rule follow


Hund rule not follow
Calculation of CFSE
Calculation of CFSE

Energy above and below Bary


center has to be same

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Calculation of CFSE
Calculation of CFSE
Calculation of CFSE
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Calculation of CFSE
Factors affecting CFSE/
Factors influencing the magnitude of 

1. Nature of CMA:
a. Same CMA with different charge: If the complexes
containing same CMA with the different charge then the
complex with the higher +ve charge of the CMA will exhibit
higher Δ value.
Exm:

b. Different CMA with the different charge:


If the complexes containing the different charge then the
complex which containing higher +ve charge at the CMA
exhibit higher Δ value.
Exm:
Factors affecting CFSE/
Factors influencing the magnitude of 

(C) Different CMA with same charge:


If the complexes containing different CMA with the same
charge then that complex which containing lower dn
configuration of CMA will exhibit higher Δ value.

(d) Principal quantum no of dn configuration:


With the increase in the Principal quantum number of dn
configuration of CMA, the value of Δ is increases.
3d -----> 4d ----> 5d the value of increases by 25 - 50%
Factors affecting CFSE/
Factors influencing the magnitude of 

2. Nature of ligands: With the increase in the strength of


the ligands present in the complexes the Δ value for the
complexes is increases.

The common ligands can be ordered on the basis of the


effect that they have on the crystal field splitting. This
ordered listing is called the spectrochemical series.
Factors affecting CFSE/
Factors influencing the magnitude of 
Spectrochemical Series
Factors affecting CFSE/
Factors influencing the magnitude of 

3. Geometry of the complex


Spectrochemical Series
Crystal field stabilization energy : Octahedral
Calculation of CFSE

∆0 < P ∆0 > P

Hund rule follow


Hund rule not follow
Calculation of CFSE
Calculation of CFSE
Calculation of CFSE
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Calculation of CFSE
Calculation of CFSE
Crystal field stabilization energy : Octahedral
Color of Transition metal complexes

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Color of Transition metal complexes

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Color of Transition metal complexes

d-d transition

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Color of Transition metal complexes

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Color of Transition metal complexes

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Color of Transition metal complexes
Example: Rank [Ti(H2O)6]3+, [Ti(CN)6]3-, [Ti(NH3)6]3+ in terms of ∆ and of
the energy of visible light absorbed.

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Distortion of octahedral complex & Jahn-Teller theorem

The Jahn-Teller effect is a geometric distortion of a non-linear


molecular system that reduces its symmetry and energy. This distortion
is typically observed among octahedral complexes where the two axial
bonds can be shorter or longer than those of the equatorial bonds.

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Jahn-Teller Distortion

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Jahn-Teller Distortion

Presence of symmetry so no
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Jahn-Teller Distortion

Absence of symmetry but


very negligible distortion 44 02/07/2024
Jahn-Teller Distortion

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d5 (high spin) d5 (low spin)

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d6 (low spin)

d6 (high spin)

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Jahn-Teller Distortion

d7 (high spin) d7 (low spin)


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d8)
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d9

Jahn-Teller distortion occur for50unsymmetrical filling eg orbital


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Jahn-Teller Distortion

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Jahn-Teller Distortion

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Jahn-Teller Distortion

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Jahn-Teller Distortion

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Crystal Field Theory(CFT)

LIMITATIONS OF CFT
1. CFT considers the splitting of d- orbital but it does not
consider the splitting of other orbitals in the ligand field
environment.
2. CFT can’t explain that how certain ligands having more
splitting power/ability while certain other ligands having
very low splitting ability.
3. According to the CFT metal ligand bond having 100% ionic
character but from the various experiment it was froved
that metal ligand bonds having certain extent of covalence
with the ionic character.

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