Rate coefficients of the HCl+OH→Cl+H2O reaction from ring polymer molecular dynamics
作者单位：Institute of Theoretical and Computational Chemistry Key Laboratory of Mesoscopic ChemistrySchool of Chemistry and Chemical Engineering Nanjing University Department of Physics International Center of Quantum and Molecular Structure Shanghai key Laboratory of High Temperature Superconductors Shanghai University Department of Chemistry and Chemical Biology University of New Mexico Synergetic Innovation Center of Quantum Information and Quantum Physics University of Science and Technology of China
会议名称：《中国化学会第30届学术年会-第四十四分会：化学动力学》
会议日期：2016年
学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学]
关 键 词：ring polymer molecular dynamics quantum effects rate coefficients
摘 要：Thermal rate coefficients at temperatures between 200 and 1000 K are calculated for the HCl + OH → Cl + HO 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 semi-classical tunneling corrections.