Rotationally mediated vibration–vibration and vibration–translation energy transfer in silane

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Abstract
Vibration–vibration (V–V) and vibration–translation (V–T) energy transfer efficiencies have been measured for the v4=1 mode of silane in collisions with He, Ar, Kr, H2, CH4, and itself, using the time‐resolved infrared double‐resonance technique. The V–V cross sections are approximately one‐third to one‐half of the Lennard‐Jones cross sections, and show a variation with the nuclear–spin symmetry state (A, E, or F) of the molecule. The ν4 V–T deactivation efficiencies are in the range 0.0001–0.002, with the polyatomic molecules being about an order of magnitude more efficient than the noble‐gas atoms. This can be quantitatively interpreted by the vibration–rotation (V–R) resonance transfer model of Poulsen et al. [J. Chem. Phys. 5 8, 3381 (1973)]. A simple breathing‐sphere model does not, however, provide a good representation of the V–T collision efficiencies for rare gas–silane collisions.

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