Journal of Chemical Physics
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.
Semenov, Alexander; Dubernet, Marie-Lise; and Babikov, Dmitri, "Mixed Quantum/Classical Theory for Inelastic Scattering of Asymmetric-top-rotor + Atom in the Body-fixed Reference Frame and Application to the H2O + He System" (2014). Chemistry Faculty Research and Publications. 352.