Journal of Chemical Physics
The mixed quantum/classical approach is applied to the problem of ro-vibrational energy transfer in the inelastic collisions of CO(v = 1) with He atom, in order to predict the quenching rate coefficient in a broad range of temperatures 5 < T < 2500 K. Scattering calculations are done in two different ways: direct calculations of quenching cross sections and, alternatively, calculations of the excitation cross sections plus microscopic reversibility. In addition, a symmetrized average-velocity method of Billing is tried. Combination of these methods allows reproducing experiment in a broad range of temperatures. Excellent agreement with experiment is obtained at 400 < T < 2500 K (within 10%), good agreement in the range 100 < T < 400 K (within 25%), and semi-quantitative agreement at 40 < T < 100 K(within a factor of 2). This study provides a stringent test of the mixed quantum/classical theory, because the vibrational quantum in CO molecule is rather large and the quencher is very light (He atom). For heavier quenchers and closer to dissociation limit of the molecule, the mixed quantum/classical theory is expected to work even better.
Semenov, Alexander; Ivanov, Mikhail V.; and Babikov, Dmitri, "Ro-vibrational Quenching of CO (v = 1) by He Impact in a Broad Range of Temperatures: A Benchmark Study Using Mixed Quantum/Classical Inelastic Scattering Theory" (2013). Chemistry Faculty Research and Publications. 271.