Evaluation of the crystal field-closure-ligand polarization interference term for the vibronic intensities of centrosymmetric coordination compounds

Abstract

A reexamination of the relative phases of the crystal field-closure and ligand polarization contributions to the intensities of individual vibronic origins shows that the interference term is appreciable and positive for the v ₃, v ₄ and v ₆ vibronic origins of the ⁴ A _2g ↔ ⁴ T _2g transition of the MnF^2- ₆ ion. We had previously reported that this term was identically zero for v ₆ but this error arose from the use of an inconsistent choice of phases in the v ₆ symmetry coordinate. A corrected table of computed dipole strengths and relative vibronic intensities is given which is in excellent agreement with experiment.