Intensity distribution in the vibronic side bands of the ?7(2 T 2g ) ? ?8(4 A 2g ) origin of ReX 6 2- doped K2PtCl6-type crystals

Intensities of vibronic transitions are calculated using an electronic vibrational coupling scheme of symmetrized and localized interactions. The model consists of an active central ion subject to a valence force field originating from nearest-neighbor displacements. The intensities of vibronic fundamentals are obtained from a generalized Lorentzian line shape function which is applied to the Γ7(2T2g) → Γ8(4A2g) transition of ReCl 6 2- and ReBr 6 2- in various cubic host crystals A2MX6 (A = Rb, Cs; M = Te, Sn, Pb; X = Cl, Br). Relative intensities of the odd vibronic side bands are calculated without knowing actual values for ligand field and spin-orbit coupling parameters, and considering only octahedral vibrational frequencies. The sidebands acquire intensity by a coupling which is cubic in the electron coordinates and linear in the nuclear normal coordinates. With some necessary approximations the present model is able to reproduce the experimental intensity distribution satisfactorily.