A symmetry-based model for selective rotational energy transfer in collisions of spherical top molecules

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Abstract
Recent state-resolved experiments have shown that rotational energy transfer in collisions of vibrationally excited spherical top molecules is remarkably selective with respect to the fine structure components of the rovibrational states. It is shown that this selectivity can be explained by means of symmetry arguments and the Harter–Patterson theory of spectral clustering. A new propensity rule, which extends the well-known symmetric top selection rule to perturbed spherical tops, is derived and shown to account well for the experimental results of Steinfeld and co-workers on 13CD4 and SiH4.

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