Crystal Field - Spin Orbit - Configuration Interaction Model

for many-electron systems

Part 1


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Crystal Field splitting of the d-type Atomic Orbitals

Typically in transition metal complexes the d-electrons are mostly localized at the central metal. In the Crystal Field Theory, a complex is modeled by a pure metal ion (no delocalization) in the electrostatic field of the rest of the molecule. It is usually assumed that the potential field is formed by the point charges located at ligands (as in ionic crystals).

Octahedral Complex

In the free ion (or highly symmetrical fild) the d-AO are 5-fold degenerate. In the pure octahedral Crystal Field (CF) the energy levels split into the eg doublet (d z2, d x2 - d y2

z2,        x2-y2

(Created with Orbital Viewer)

 and the t2g triplet (d xy, d xz, d yz):

dxy,   dxz,   dyz

The eg subset is shifted upward in energy, is not populated for low-spin (strong CF) complexes  and is not taken into account in subsequent consideration.

Lowing the complex symmetry lead to further splitting in the triplet. In C4v or D4h symmetry one state split from the two others. Further lowing of symmetry lifts the degeneracy at all. 

CF splitting of the d-type Orbitals 

The d-AO energy structure can be modeled using the program CFSOCI 1 .



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