Rate Coefficients of the HCl + OH → Cl + H2O Reaction from Ring Polymer Molecular Dynamics
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- 作者：Junxiang Zuo ; Yongle Li ; Hua Guo ; Daiqian Xie
- 刊名：Journal of Physical Chemistry A
- 出版年：2016
- 出版时间：May 26, 2016
- 年：2016
- 卷：120
- 期：20
- 页码：3433-3440
- 全文大小：418K
- 年卷期：0
- ISSN：1520-5215
文摘
Thermal rate coefficients at temperatures between 200 and 1000 K are calculated for the HCl + OH → Cl + H2O reaction on a recently developed permutation invariant potential energy surface, using ring polymer molecular dynamics (RPMD). Large deviations from the Arrhenius limit are found at low temperatures, suggesting significant quantum tunneling. Agreement with available experimental rate coefficients is generally satisfactory, although the deviation becomes larger at lower temperatures. The theory–experiment discrepancy is attributed to the remaining errors in the potential energy surface, which is known to slightly overestimate the barrier. In the deep tunneling region, RPMD performs better than traditional transition-state theory with semiclassical tunneling corrections.