Document Type

Article

Publication Date

2014

Source Publication

Journal of Chemical Physics

Source ISSN

0021-9606

Abstract

The mixed quantum/classical theory (MQCT) for inelastic molecule-atom scattering developed recently [A. Semenov and D. Babikov, J. Chem. Phys.139, 174108 (2013)] is extended to treat a general case of an asymmetric-top-rotor molecule in the body-fixed reference frame. This complements a similar theory formulated in the space-fixed reference-frame [M. Ivanov, M.-L. Dubernet, and D. Babikov, J. Chem. Phys.140, 134301 (2014)]. Here, the goal was to develop an approximate computationally affordable treatment of the rotationally inelastic scattering and apply it to H2O + He. We found that MQCT is somewhat less accurate at lower scattering energies. For example, below E = 1000 cm−1 the typical errors in the values of inelastic scattering cross sections are on the order of 10%. However, at higher scattering energies MQCT method appears to be rather accurate. Thus, at scattering energies above 2000 cm−1 the errors are consistently in the range of 1%–2%, which is basically our convergence criterion with respect to the number of trajectories. At these conditions our MQCT method remains computationally affordable. We found that computational cost of the fully-coupled MQCT calculations scales as n 2, where n is the number of channels. This is more favorable than the full-quantum inelastic scattering calculations that scale as n 3. Our conclusion is that for complex systems (heavy collision partners with many internal states) and at higher scattering energies MQCT may offer significant computational advantages.

Comments

Published version. Journal of Chemical Physics, Vol. 141, No. 11 (2014): 114304. DOI. © 2014 American Institute of Physics. Used with permission.

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