Assignments in the ultraviolet spectra of MoF6 and WF6

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Abstract
The ultraviolet absorption spectra of gaseous MoF6 and WF6 were measured from 1100 to 2500 Å (40 000–90 000 cm−1). Assignments of the observed transitions, based on a qualitative molecular orbital diagram and comparisons of predicted and observed relative band intensities, are proposed. The ligand field splitting of the Mo(4)d orbitals is estimated to be 40 000 cm−1. A comparison of the uv absorption and photoelectron ionization spectrum of WF6 suggests that for this molecule the ligand field approximation is excellent: There are no interactions between the ligand and metal orbitals. Many of the observed transitions manifest progressions in the a1 vibrational mode from which expansions of the molecular octahedron in each of the assorted electronic excited states is deduced.