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

Abstract

Spin-orbit coupling and vibronic coupling are both closely related to orbital degeneracy of electronic states. Both types of coupling play significant roles in determining properties of heavy element compounds and shall be treated on the same footing. In this work, we derive a unified one-electron Hamiltonian formalism for spin-orbit and vibronic interactions for systems in all axial symmetries. The one-electron formalism is usually adequate as the spin-orbit interaction can often be approximated as a one-electron interaction. For the first time, the formalism covers spin-orbit and vibronic couplings in all axial symmetries from C1 to D∞h, arbitrary types of vibrational modes in those symmetries, and an arbitrary number of those modes and gives Hamiltonian expansions up to an arbitrary order.