Unified one-electron Hamiltonian formalism of spin-orbit Jahn-Teller and pseudo-Jahn-Teller problems in tetrahedral and octahedral symmetries.

Abstract

Heavy element compounds with high symmetries often feature both spin-orbit coupling and vibronic coupling. This is especially true for systems with tetrahedral and octahedral symmetries, whose electronic states may be threefold degenerate and experience complicated Jahn-Teller and pseudo-Jahn-Teller interactions. To accurately describe these interactions, high quality spin-orbit vibronic Hamiltonian operators are needed. In this study, we present a unified one-electron Hamiltonian formalism for spin-orbit vibronic interactions for systems in all tetrahedral and octahedral symmetries. The formalism covers all spin-orbit Jahn-Teller and pseudo-Jahn-Teller problems in the symmetries with arbitrary types and arbitrary numbers of vibrational modes and generates Hamiltonian expansion formulas of arbitrarily high order.