Mixed quantum/classical calculations of rotationally inelastic scattering in the CO + CO system: a comparison with fully quantum results.

Abstract

An updated version of the CO + CO potential energy surface from [R. Dawes, X. G. Wang and T. Carrington, J. Phys. Chem. A 2013, 117, 7612] is presented, that incorporates an improved treatment of the asymptotic behavior. It is found that this new surface is only slightly different from the other popular PES available for this system in the literature [G. W. M. Vissers, P. E. S. Wormer and A. Van Der Avoird, Phys. Chem. Chem. Phys. 2003, 5, 4767]. The differences are quantified by expanding both surfaces over a set of analytic functions and comparing the behavior of expansion coefficients along the molecule-molecule distance R. It is shown that all expansion coefficients behave similarly, except in the very high energy range at small R where the PES is repulsive. That difference has no effect on low collision-energy dynamics, which is explored via inelastic scattering calculations carried out using the MQCT program which implements the mixed quantum/classical theory for molecular energy exchange processes. The validity of MQCT predictions of state-to-state transition cross sections for CO + CO is also tested by comparison against full-quantum coupled-states calculations. In all cases MQCT gives reliable results, except at very low collision energy where the full-quantum calculations predict strong oscillations of state-to-state transition cross sections due to resonances. For strong transitions with large cross sections, the results of MQCT are reliable, especially at higher collision energy. For weaker transitions, and lower collision energies, the cross sections predicted by MQCT may be up to a factor of 2-3 different from those obtained by full-quantum calculations.