OsF₆ energy levels and vibronic coupling in the (d_t2g)² configuration

Abstract

Electronic and vibronic energy levels of the (d_{t 2g} )² configuration of OsF₆ are studied using electronic Raman scattering and absorption spectroscopy. The ground state has been identified as E_g (crystal field split by ∼28 cm⁻¹) and the first excited state is T_1g with crystal energy levels at 14, 28, and 40 cm⁻¹. The three other regions of the spectrum that have been observed are at 4000 cm⁻¹, 8000 cm^-1, and 17 000 cm⁻¹ covering the remaining (d_{t 2g}) ² configuration leveIs. The 4000 cm⁻¹ band consists of A_1g and T_1g electron states which do not interact strongly through vibronic coupling. The T_1g electronic state evidences a strong (D∼2·2) linear Jahn-Teller effect for ν₅ and an observable Jahn-Teller effect for ν₂. The band at 8000 cm⁻¹ consists of E_g and T_2g electronic states; it is so complex and strongly coupled that little information can be extracted from the absorption data concerning the Jahn-Teller interaction in this 5-fold degenerate manifold. The feature at 17 000 cm⁻¹ is an A_1g electronic state and its elucidation follows normal behaviour found in other hexafluoride spectra.

Supported in part by ONR and ARO-D.

Supported in part by ONR and ARO-D.

Notes

Supported in part by ONR and ARO-D.