Vibrational relaxation of CO (n1=1) in collision with ortho, para H2 is studied quantum mechanically, with the rotational degree of freedom of H2 included. This represents extension of our earlier study [Ref. 11, J. Chem. Phys. 82, 236 (1985)], where H2 was treated as a structureless particle. The potential surface, described in detail in Ref. 11, consists of a SCF part, which includes explicitly the variation with the CO bond distance, and a damped long range dispersion contribution. The relaxation cross sections are calculated within the infinite order sudden approximation (IOSA) for CO rotation and within the coupled states approximation (CSA) for H2 rotation. Many of the trends clearly present in the cross sections can be understood in terms of the distorted wave approximation (DWA). The calculated relaxation rates in para H2 agree well (within a factor of 2) with the experimental results. However, judging from a limited number of calculated cross sections for relaxation in ortho H2, the ortho H2 relaxation rates would be comparable in magnitude to the para rates, in disagreement with experiment. Extensive comparison is made with the work of Poulsen and Billing (Ref. 12) and a number of significant, even qualitative differences regarding magnitude of some simultaneous CO vibrational and H2 rotational transitions are discussed.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry