Excited vibrational state microwave spectra, structure, and force-field of trifluorosilane

Hoy, A. R., Bertam, M. and Mills, I. (1973) Excited vibrational state microwave spectra, structure, and force-field of trifluorosilane. Journal of Molecular Spectroscopy, 46 (3). pp. 429-447. ISSN 0022-2852 doi: 10.1016/0022-2852(73)90055-6

Abstract/Summary

The J = 2−1 microwave spectrum of six isotopic species of HSiF3 has been observed and assigned in excited states of five of the six fundamental vibrations. The assignment is based on relative intensities, double resonance experiments, and trial anharmonic force constant calculations. Analysis of the spectra leads to experimental values for five of the constants, all three l-doubling constants qt, one Fermi resonance constant φ233, and one zeta constant. The harmonic force field has been refined to all the available data on vibration wavenumbers, centrifugal distortion constants, and zeta constants. The cubic anharmonic force field has been refined to the data on and qt constants, using two models: a valence force model with two cubic force constants for SiH and SiF stretching, and a more sophisticated model. With the help of these calculations, the following equilibrium structure has been determined: re(SiH) = 1.4468(±5) Å, re(SiF) = 1.5624(±1) Å, HSiF = 110.64(±3)°,