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Quasi-classical Trajectory Study of F+H2O→HF+OH Reaction: Influence of Barrier Height, Reactant Rotational Excitation, and Isotopic Substitution (cited: 4)
Jun Li,Hua Guo*
Author NameAffiliationE-mail
Jun Li Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA  
Hua Guo* Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA hguo@unm.edu 
Abstract:
The reaction dynamics of the F+H2O/D2O→HF/DF+OH/OD are investigated on an ac-curate potential energy surface (PES) using a quasi-classical trajectory method. For bothisotopomers, the hydrogen/deuterium abstraction reaction is dominated by a direct rebound mechanism over a very low “reactant-like” barrier, which leads to a vibrationally hot HF/DF product with an internally cold OH/OD companion. It is shown that the lowered reaction barrier on this PES, as suggested by high-level ab initio calculations, leads to a much better agreement with the experimental reaction cross section, but has little impact on the product state distributions and mode selectivity. Our results further indicate that rotational exci-tation of the H2O reactant leads to significant enhancement of the reactivity, suggesting a strong coupling with the reaction coordinate.
Key words:  Reaction dynamics, Potential energy surface, Isotopic effect
FundProject:
F+H2O/D2O→HF+OH反应的准经典轨迹研究:能垒、反应物转动激发和同位素取代的影响 (cited: 4)
李军,郭华*
摘要:
在新构建的含旋轨耦合校正的FH2O基态势能面上,采用准经典轨迹方法详细研究了F+H2O/D2O→HF/DF+OH/OD的反应动态学.氢和氘抽取反应经过较低的类反应物过渡态直接发生反应,生成振动激发的HF/DF和内能较低的OH/OD产物.由于新构建的势能面能垒较低,得到的积分反应截面与实验值吻合.但新势能面对产物态分布和模式选择性影响较小.理论计算结果显示H2O的转动态激发对反应有很强的促进作用,说明其与反应坐标耦合紧密.
关键词:  反应动力学,势能面,同位素效应
DOI:10.1063/1674-0068/26/06/627-634
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