Full-dimensional quantum wave packet study of collision-induced vibrational relaxation between para-H2

被引:26
作者
Lin, SY [1 ]
Guo, H [1 ]
机构
[1] Univ New Mexico, Dept Chem, Albuquerque, NM 87131 USA
基金
美国国家科学基金会;
关键词
D O I
10.1016/S0301-0104(03)00020-X
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
An accurate quantum investigation of vibrational relaxation induced by collision: para-H-2(v(1) = 1, j(1) = 0) +para-H-2(v(2) = 0, j(2) = 0) --> para-H-2(v'(1) = 0, j'(1)) + para-H-2(v'(2) = 0, j'(2)), is presented. The Hamiltonian within the coupled-states approximation is discretized in a mixed grid/basis representation and its action is computed in appropriate representations facilitated by a series of one-dimensional pseudo-spectral transformations. Furthermore, the parity and diatomic exchange symmetry are adapted to improve efficiency. S-matrix elements at numerous collision energies up to 2.2 eV are calculated from the Fourier transform of correlation functions obtained from the Chebyshev propagation. Partial wave contributions from J = 0 to 90 are obtained explicitly. Finally, thermal rate constants are computed over a wide range of temperatures (0-3500 K) and compared with available experimental measurements. In addition, the effect of initial rotational excitation on the relaxation probability is investigated. (C) 2003 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:191 / 199
页数:9
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