Ligand field theoretical considerations

The phenomenon of the thermal spin transition, as observed for octahedral transition metal complexes having a d 4 to d 7 electronic configuration, can be fully rationalised on the basis of ligand field theory. In order toarrive at a self-consistent description of the vibronic structure of spin crossover compounds, it is essential to take into account the fact that the population of anti-bonding orbitals in the high-spin state results in a substantially larger metal-ligand bond length than for the low-spin state. Whereas the electron-electron repulsion is not affected to any great extent by such a bond length difference, the ligand field strength for iron(II) spin crossover compounds can be estimated to be almost twice as large in the low-spin state as compared to the one for the high-spin state. In fact, the dependence of the ligand field strength on the metal-ligand distance may be considered the quantum mechanical driving force for the spin crossover phenomenon.