Tensorial development of the rovibronic Hamiltonian and transition moment operators for octahedral molecules

Abstract

We present a development of the Hamiltonian, dipole moment and polarizability operators of octahedral XY6 molecules in a degenerate electronic state. These rovibronic operators are written with the aid of a tensorial formalism derived from the one already used in Dijon in the case of molecules in a non-degenerate electronic state. Electronic operators are defined from the group theory properties. Transition moment operators are introduced in order to consider rovibronic transitions. Spectrum simulations are made thanks to a new version of the HTDS sofware [J. Quant. Spectrosc. Radiat. Transfer 66 (2000) 16] used for the calculation of rovibrational spectra.