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Lecture 10

This document discusses electron configurations of transition metal ions and how their energy levels split in different ligand field environments. It provides: 1) Tables showing how free ion terms split into Russel-Saunders terms and how terms further split in octahedral vs. tetrahedral ligand fields. 2) Diagrams called "Orgel diagrams" that show how term energies change with increasing ligand field strength, allowing prediction of absorption bands. 3) Examples of Orgel diagrams for d1, d2, d3 ground states and how they relate to observed absorption features in electronic spectra.

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Debopam Ray
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42 views

Lecture 10

This document discusses electron configurations of transition metal ions and how their energy levels split in different ligand field environments. It provides: 1) Tables showing how free ion terms split into Russel-Saunders terms and how terms further split in octahedral vs. tetrahedral ligand fields. 2) Diagrams called "Orgel diagrams" that show how term energies change with increasing ligand field strength, allowing prediction of absorption bands. 3) Examples of Orgel diagrams for d1, d2, d3 ground states and how they relate to observed absorption features in electronic spectra.

Uploaded by

Debopam Ray
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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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Free Ion Spectroscopic Terms for dn Configurations

 Electron-electron repulsions cause a given electron configuration to be split into


terms.

▪ Terms: Energy levels of atoms or ions that arise due to inter-electronic repulsions.
Configuration Russel-Saunders Terms
d0, d10 1
S
d 1, d 9 2
D
d 2, d 8 3
F, 3P, 1G, 1D, 1S
d 3, d 7 4
F, 4P, 2H, 2G, 2F, 2D, 2D, 2P
d 4, d 6 5
D, 3H, 3G, 3F, 3F, 3D, 3P, 3P, 1I, 1G, 1G, 1F, 1D, 1D, 1S, 1S
d5 6
S, 4G, 4F, 4D, 4P, 2I, 2H, 2G, 2G, 2F, 2F, 2D, 2D, 2D, 2P, 2S

 Ground state terms are highlighted in bold.

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Splitting of Free Ion Terms In Octahedral Ligand Field

Term Components Formed by Splitting in Octahedral Ligand Field


S A1g
P T1g
D Eg+T2g
F A2g+T1g+T2g
G A1g+Eg+T1g+T2g
H Eg+T1g+T2g+T2g
I A1g+A2g+Eg+T1g+T2g+T2g

 s (spherically symmetrical) and p orbitals do not split in octahedral ligand field.


Thus, S and P terms will be unaffected and they give A1 and T1 terms, respectively.
 Orbital multiplicity of the free ion terms is retained in the aggregate of component
terms. Thus, an F term (L = 3, orbital multiplicity = 7) splits into one singlet (A 2) and
two triplet (T1 and T2) terms, maintaining a total orbital degeneracy of (1+3+3) or 7.
 Spin multiplicity of the term and its components are same because the spin state of
an electron is not disturbed by the symmetry (Oh, Td, etc.) of ligand field.
2
Splitting of D and F Terms in Tetrahedral and Octahedral Symmetries

 Hole concept suggests an inversion of term splitting between dn and d10-n


configurations.

 For example, a d9 metal ion has an electron vacancy or “hole” in its d level and thus
can be regarded as the inverse of a d1 arrangement.

 An inversion of term splitting also occurs between tetrahedral and octahedral


symmetries. Since ligand fields of these two symmetries produce inverse splitting
patterns for d orbitals, any free ion term will also split into new terms by tetrahedral
and octahedral fields, but the energy ordering will be opposite for two symmetries.

3
Orgel Diagrams

 Orgel diagrams show the energies of terms as a function of ligand field strength.

 With the help of Orgel diagrams, the number of spin allowed absorption bands can
be predicted in the UV/Visible spectrum of a complex.

Orgel Diagram for Free Ion D Ground State

 From this diagram, we can see why one absorption is observed in the electronic
spectra of d1, d4, d6 and d9 octahedral and tetrahedral complexes.
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Orgel Diagram for Free Ion F Ground State

 From this diagram, we can see why three absorptions are observed in the electronic
spectra of d2, d3, d7 and d8 octahedral and tetrahedral complexes.
 Labels on Orgel diagrams do not include spin multiplicity designations. Spin
multiplicities must be added when discussing specific transitions. 5
Orgel Diagram for Free Ion F Ground State
▪ At increased field strengths, the lines describing the T1g(F) and T1g(P) terms curve repel away
from one another; there is interaction between terms of the same symmetry and they are not
allowed to cross (non-crossing rule). The condition of no interaction is shown by dashed lines.

Electronic Spectra of 3d Transition Metal Complexes [M(H2O)6]2+

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Electronic Spectra of 3d Transition Metal Complexes [M(H2O)6]2+

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