Influence of the Jahn–Teller effect on the g-tensor of the spin-orbit quartet in three-coordinate D3h structures

Abstract

Theoretical calculations of g-tensor components for the spin–orbit quartet, which arises as the ground state in three-coordinate d9 complexes and low-spin d7 complexes of D3h symmetry, have been made on the assumption that the spin–orbit interaction is commensurable with the electron-vibrational interaction. The calculations were carried out within the framework of crystal field theory using representations of the hole formalism. The analytical expressions for g-tensor components were obtained limited to first-order terms. It was shown that the account of the electron–vibrational interaction in the excited quartet only provides three-axial anisotropy for the g-tensor. It was shown that the g-tensor rotates in the plane of the three-coordinate structure with consensual motion of the atoms. The resulting expressions for the g-factor components are in good agreement with experimental data. Being universal for a wide range of contributions of the vibronic and spin–orbit interactions, these expressions essentially fill the gap in studying structures of coordination compounds.