Noble Gas Collision Induced Vibrational Relaxation of (v=1) para-H2

Chemistry;vibrational relaxation;molecular scattering;H2-Ar;H2-Ne;H2-He

Weir, Douglas

University of Waterloo

关键词: Chemistry;    vibrational relaxation;    molecular scattering;    H2-Ar;    H2-Ne;    H2-He;   

Others  :  https://uwspace.uwaterloo.ca/bitstream/10012/1227/1/dweir2001.pdf

瑞士|英语

来源: UWSPACE Waterloo Institutional Repository

【 摘 要 】

Close coupling scattering calculations have been conducted for the para spin modification of H₂-{He, Ne and Ar}.The XC(fit) potential energy surfaces for H₂-Ne and H₂-Ar have been used for calculations for these two systems, while a newly fitted version of the Schaefer and Kohler potential energy surface was used for the H₂-He system.The fitting procedure employs nine modified Lennard-Jones oscillator functions to describe accurately 90% of the original tabulated potential energy surface to better than 12% error. The scattering calculations for H₂-Arfailed at higher energies due to the presence of a previously undocumented potential energy surface turn-over at R less than 1.0 Angstroms.Manifold-to-manifold v=1 vibrational relaxation calculations for each of these systems are compared with other experimental and theoretical calculations.These comparisons demonstrate a common discrepancy between previous calculations and the current calculations for each system.The current vibrational relaxation rate constants are generally too small when compared to low temperature values of Audibert et al. and Orlikowski, and the high temperature values obtained by Flower et al. and Dove andTeitelbaum.The current calculations indicate the presence of a dramatic up-turn in the low temperature H₂-He rate constants.Other experimental and theoretical treatments do not exhibit this same up-turn, which is puzzling.A set of follow-up calculations featuring a larger basis set (such as the {16,12,10,8} Flower et al. basis set) and a larger manifold of included relaxation pathways are needed to improve these calculations.