Angular overlap calculations of the spin Hamiltonian parameters of transition metal ions in low symmetry environments. High spin iron(II), iron(III) and manganese(III)

Abstract

A non-perturbative method is presented for the calculation of spin Hamiltonian parameters of d″ ions, 1 ≤ n ≤ 9. In its present form, it allows the calculation of the linear Zeeman and the second- and fourth-order zero-field spin Hamiltonian parameters. Symmetry restraints can easily be applied but application to non-symmetric molecules with determination of all 20 spin Hamiltonian parameters does not present particular difficulties. The model is based on a direct comparison of the spin Hamiltonian energies with the ligand field energies including spin-orbit coupling and Zeeman interaction of all-order perturbation. The model is applied to compute the spectromagnetic parameters of high spin iron(III), high spin iron(II) and high spin manganese(III) model chromophores.