The high-resolution infrared spectrum of Si₂H₆: rotation–torsion analysis of the ν₅ and ν₇ fundamentals, and torsional splittings in the degenerate vibrational states

Abstract

The infrared active ν₇ and ν₅ fundamentals of disilane, coupled by an x,y Coriolis interaction, have been analysed on a Fourier transform spectrum between 2120 and 2225 cm⁻¹, at the Doppler limited spectral resolution. A Fermi resonance with 2ν ₂ + ν₉ affects the Δ K = 1 side of ν₇, and both ν₇ and ν₅ show the effects of several additional localized perturbations. Line splittings in the ν₅ transitions are not observed, showing that the torsional splitting in the ν₅ excited state and in the vibrational ground state are almost equal. The intrinsic torsional splitting of ν₇ is found to be smaller than in the ground vibrational state by 0.0085 cm⁻¹. This splitting value and those found for the other two infrared active degenerate fundamentals, ν₈ and ν₉, follow the trend expected from our theoretical predictions. Exploratory numerical calculations show that the decrease of the torsional splittings, observed in the fundamental degenerate vibrational states of disilane, can actually be accounted for by the head–tail and torsional Coriolis coupling of all the degenerate vibrational fundamentals, in several torsional states.

Notes

We have verified through cumbersome transformations that the results of [24] are correct, including the occurrence of the terms with coefficients f  ⁽⁶⁾, which do contribute to H ⁽²⁾. The occurrence of such terms with symmetry coordinates was incorrectly questioned in [6]