Vibrational Spectroscopy of Tungsten(VI) Chlorides: WCl ₆ and WOCl ₄

Tungsten (VI) hexachloride, WCl₆, and tungsten (VI) oxytetrachloride, WOCl₄, are of interest in a variety of technological applications. In the present work, complete vibrational assignments are provided for both molecules in the "free" state (i.e., in the gas phase or in solution) and in the solid state. The first inelastic neutron scattering spectra of both molecules in the solid state are recorded. The assignments are supported by density functional theory calculations. In all cases, the W-Cl stretching modes occur in the 300-400 cm^-1 range, and the Cl-W-Cl bending modes in the 100-250 cm^-1 range.