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Title: Quantum dynamics study of the reaction HD+OH{r_arrow}H+DOH, D+HOH

Abstract

Accurate time-dependent (TD) quantum wavepacket calculations are reported for the combustion reaction HD+OH. Due to the lack of symmetry, the HD+OH reaction has roughly twice the number of channels of the corresponding H{sub 2}+OH reaction and produces two distinguishable products--HOH and HOD. In order to make the TD calculation possible on workstations with limited memories, we employed a normalized quadrature scheme in the wavepacket propagation by the split-operator propagator. The normalized quadrature scheme eliminates the need to store large matrices during the wavepacket propagation while preserving the unitarity of the split-operator propagator and producing numerically stable results. This approach made TD dynamics calculations possible on small-memory workstations for the title reaction and for other polyatomic reactions. Reaction probabilities, cross sections, rate constants, and reaction branching ratios are reported in this paper for the title reaction. The observed strong dependence of the reaction probabilities on the reactive HD rotation and the relative weak dependence on the nonreactive OH rotation are explained in terms of a steric effect. The isotope effect in the branching ratio is examined and physical explanation is given for the observed branching ratio at low and high kinetic energies.

Authors:
;  [1]; ; ;  [2]
  1. Department of Chemistry, New York University, New York, New York 10003 (United States)
  2. Department of Physics, Shandong Teacher`s University, Jinan, Shandong (China)
Publication Date:
OSTI Identifier:
45981
DOE Contract Number:  
FG02-94ER14453
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 102; Journal Issue: 19; Other Information: PBD: 15 May 1995
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; HYDROXYL RADICALS; CHEMICAL REACTION KINETICS; COMBUSTION KINETICS; HYDROGEN DEUTERIDE; DEUTERIUM; CHEMICAL REACTION YIELD; COMBUSTION PRODUCTS; HYDROGEN; WATER; HEAVY WATER; DYNAMICS; COMPUTERIZED SIMULATION; ONE-DIMENSIONAL CALCULATIONS; COMBUSTION; BRANCHING RATIO; QUANTUM MECHANICS; CROSS SECTIONS

Citation Formats

Zhang, D.H., Zhang, J.Z.H., Zhang, Y., Wang, D., and Zhang, Q. Quantum dynamics study of the reaction HD+OH{r_arrow}H+DOH, D+HOH. United States: N. p., 1995. Web. doi:10.1063/1.469052.
Zhang, D.H., Zhang, J.Z.H., Zhang, Y., Wang, D., & Zhang, Q. Quantum dynamics study of the reaction HD+OH{r_arrow}H+DOH, D+HOH. United States. doi:10.1063/1.469052.
Zhang, D.H., Zhang, J.Z.H., Zhang, Y., Wang, D., and Zhang, Q. Mon . "Quantum dynamics study of the reaction HD+OH{r_arrow}H+DOH, D+HOH". United States. doi:10.1063/1.469052.
@article{osti_45981,
title = {Quantum dynamics study of the reaction HD+OH{r_arrow}H+DOH, D+HOH},
author = {Zhang, D.H. and Zhang, J.Z.H. and Zhang, Y. and Wang, D. and Zhang, Q.},
abstractNote = {Accurate time-dependent (TD) quantum wavepacket calculations are reported for the combustion reaction HD+OH. Due to the lack of symmetry, the HD+OH reaction has roughly twice the number of channels of the corresponding H{sub 2}+OH reaction and produces two distinguishable products--HOH and HOD. In order to make the TD calculation possible on workstations with limited memories, we employed a normalized quadrature scheme in the wavepacket propagation by the split-operator propagator. The normalized quadrature scheme eliminates the need to store large matrices during the wavepacket propagation while preserving the unitarity of the split-operator propagator and producing numerically stable results. This approach made TD dynamics calculations possible on small-memory workstations for the title reaction and for other polyatomic reactions. Reaction probabilities, cross sections, rate constants, and reaction branching ratios are reported in this paper for the title reaction. The observed strong dependence of the reaction probabilities on the reactive HD rotation and the relative weak dependence on the nonreactive OH rotation are explained in terms of a steric effect. The isotope effect in the branching ratio is examined and physical explanation is given for the observed branching ratio at low and high kinetic energies.},
doi = {10.1063/1.469052},
journal = {Journal of Chemical Physics},
number = 19,
volume = 102,
place = {United States},
year = {1995},
month = {5}
}