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Title: Rotational quenching of H{sub 2}O by He: Mixed quantum/classical theory and comparison with quantum results

The mixed quantum/classical theory (MQCT) formulated in the space-fixed reference frame is used to compute quenching cross sections of several rotationally excited states of water molecule by impact of He atom in a broad range of collision energies, and is tested against the full-quantum calculations on the same potential energy surface. In current implementation of MQCT method, there are two major sources of errors: one affects results at energies below 10 cm{sup −1}, while the other shows up at energies above 500 cm{sup −1}. Namely, when the collision energy E is below the state-to-state transition energy ΔE the MQCT method becomes less accurate due to its intrinsic classical approximation, although employment of the average-velocity principle (scaling of collision energy in order to satisfy microscopic reversibility) helps dramatically. At higher energies, MQCT is expected to be accurate but in current implementation, in order to make calculations computationally affordable, we had to cut off the basis set size. This can be avoided by using a more efficient body-fixed formulation of MQCT. Overall, the errors of MQCT method are within 20% of the full-quantum results almost everywhere through four-orders-of-magnitude range of collision energies, except near resonances, where the errors are somewhat larger.
Authors:
 [1] ;  [2] ;  [1] ;  [3]
  1. PSL Research University, Observatoire de Paris, Sorbonne Universités, UPMC Univ Paris 06, ENS, UCP, CNRS, UMR8112, LERMA, 5 Place Janssen, 92195 Meudon (France)
  2. (United States)
  3. Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201-1881 (United States)
Publication Date:
OSTI Identifier:
22253338
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 13; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COLLISIONS; CROSS SECTIONS; EXCITED STATES; HELIUM; POTENTIAL ENERGY; QUENCHING; WATER