A Tensorial Formalism Adapted to the Rovibronic Couplings in the Colored Hexafluorides: Application to the ν5(F2g) and ν3(F1u) Modes

Abstract

A tensorial formalism adapted to the case of transition-metal hexafluorides in a degenerate electronic state has been developed on the basis of preceding works about spherical-top molecules in a nondegenerate electronic state. We have introduced electronic operators constructed using group theory features and some physical considerations. Vibronic couplings (Jahn–Teller effect, etc.) have been reviewed for the triply degenerate vibrational modes ν5(F2g) and ν3(F1u) leading to the identification of the main vibronic parameters. For the first time, an effective rovibronic Hamiltonian as well as the effective transition moment operators (dipole moment and polarizability) for rovibronic transitions have been studied qualitatively thanks to the tensorial algebra properties.