Analysis of the Fourier transform and diode laser spectra of the ν<inf>3</inf> fundamental of PuF<inf>6</inf>

Abstract

A detailed analysis of the ν3 band of PuF6 is presented. The P, Q, and R branches of the fundamental transition and of several hot bands have been observed for a cooled gas sample of PuF6 at very low pressure in a long path length cell. Both a Fourier transform spectrometer (resolution 6 × 10-3 cm-1) and a diode laser (resolution 4 × 10-4 cm-1) have been used. Wavenumbers of the rotational transitions, measured on the diode spectra, have led to accurate values for the band origin and the rotational line spacing constant. Octahedral fine-structure manifolds in the P and R branches, for low to moderate values of J, have yielded a value of the splitting parameter. However, in the high-J manifolds and throughout the entire Q branch, the fine structure deviates substantially from theory. These discrepancies are apparently the result of accidental resonances with rotational levels of one or two neighboring vibrational states. © 1988.