Importance of Anharmonicity,Recrossing Effects,and Quantum Mechanical Tunneling in Transition State Theory with Semiclassical Tunneling.A Test Case:The H_2+Cl Hydrogen Abstraction Reaction

Jorge A.Sanson; Maria-Luz Sanchez; Jose C.Corchado

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Importance of Anharmonicity,Recrossing Effects,and Quantum Mechanical Tunneling in Transition State Theory with Semiclassical Tunneling.A Test Case:The H_2+Cl Hydrogen Abstraction Reaction

机译：半过渡态在过渡态理论中非谐性，交叉效应和量子力学隧穿的重要性。一个测试案例：H_2 + Cl氢提取反应

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The hydrogen abstraction reaction from H_2 by the Cl atom is studied by means of the variational transition state theory with semiclassical tunneling coefficients on the BW2 potential energy surface.Vibrational anharmonicity and coupling between the bending modes are taken into account.The occurrence of trajectories that recross the transition state is estimated by means of the canonical unified statistical method and by classical trajectories calculations.Different semiclassical methods for tunneling calculations are tested.Our results show that anharmonicity has a small but nonnegligible effect on the thermal rate constants,recrossing can be neglected,and tunneling is adequately described by the least-action approximation,and less successfully by the large-curvature version 3 approximation.However,the large-curvature version 4 and small-curvature approximations lead to a severe underestimation of tunneling.Thermal rate constants calculated using transition state theory including anharmonicity and tunneling agree very well with accurate quantal thermal rate constants over a wide temperature range,although the improvement over the harmonic transition state theory with the microcanonically optimized semiclassical tunneling approximation (based on version 3 of the large-curvature tunneling method) used in a previous study of this reaction is only marginal.

机译：利用半经典隧穿系数的变迁过渡态理论，研究了由Cl原子从H_2吸收氢的反应，并考虑了振动非谐和弯曲模式之间的耦合。通过规范的统一统计方法和经典的轨迹计算方法来估算过渡态。测试了不同的半经典方法进行隧道计算。我们的结果表明，非谐性对热速率常数的影响很小但不可忽略，可以忽略交叉。最小作用近似可充分描述隧道效应，大曲率近似3不能很好地描述隧道效应，但是大曲率近似4和小曲率近似会导致隧道效应的严重低估。过渡态理论，包括anha尽管在微通道中使用了微经典优化的半经典隧穿近似（基于大曲率隧穿方法的第3版），但谐波和过渡态与在宽温度范围内精确的定量热速率常数非常吻合。以前对此反应的研究仅是微不足道的。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2006年第2期|共11页
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Jorge A.Sanson; Maria-Luz Sanchez; Jose C.Corchado;
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1. Importance of Anharmonicity,Recrossing Effects,and Quantum Mechanical Tunneling in Transition State Theory with Semiclassical Tunneling.A Test Case:The H_2+Cl Hydrogen Abstraction Reaction [J] . Jorge A.Sanson, Maria-Luz Sanchez, Jose C.Corchado The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2006,第2期

机译：半过渡态在过渡态理论中非谐性，交叉效应和量子力学隧穿的重要性。一个测试案例：H_2 + Cl氢提取反应
2. High-level direct-dynamics variational transition state theory calculations including multidimensional tunneling of the thermal rate constants, branching ratios, and kinetic isotope effects of the hydrogen abstraction reactions from methanol by atomic hydrogen [J] . Meana-Pa?eda R., Truhlar D.G., Fernández-Ramos A. The Journal of Chemical Physics . 2011,第9期

机译：高级直接动力学变分过渡态理论计算，包括多维速率隧穿过程中的热速率常数，支化比和原子氢从甲醇中吸氢反应的动力学同位素效应
3. High-level direct-dynamics variational transition state theory calculations including multidimensional tunneling of the thermal rate constants, branching ratios, and kinetic isotope effects of the hydrogen abstraction reactions from methanol by atomic hydrogen [J] . Meana-Pa?eda R., Truhlar D.G., Fernández-Ramos A. The Journal of Chemical Physics . 2011,第9期

机译：高级直接动力学变分过渡态理论计算，包括多维速率隧穿过程中的热速率常数，支化比和原子氢从甲醇中吸氢反应的动力学同位素效应
4. A THEORETICAL ANALYSIS OF THE CH_3 + H REACTION: ISOTOPE EFFECTS, THE HIGH-PRESSURE LIMIT, AND TRANSITION STATE RECROSSING [C] . STEPHEN J. KLIPPENSTEIN, YURI GEORGIEVSKII, LAWRENCE B. HARDING Twenty-Ninth International Symposium on Combustion Hokkaido University . 2002

机译：CH_3 + H反应的理论分析：同位素效应，高压极限和过渡态换向
5. Chemical precedent studies probing quantum-mechanical tunneling in hydrogen abstractions facilitated by coenzyme B(12). [D] . Doll, Kenneth Michael. 2003

机译：化学先例研究在辅酶B（12）促进的氢提取中的量子力学隧穿。
6. Computational Kinetics by Variational Transition State Theory with Semiclassical Multidimensional Tunneling: Direct Dynamics Rate Constants for the Abstraction of H from CH3OH by Triplet Oxygen Atoms [O] . Rubén Meana-Pañeda, Xuefei Xu, He Ma, -1

机译：基于半经典多维隧穿的变分过渡态理论的计算动力学：三重态氧原子从CH3OH提取H的直接动力学速率常数
7. Effects of Non-Adiabatic Transitions on Proton Dynamics(4) Quantum chaos and semiclassical theory in molecular science and nuclear theory, Chaos and Nonlinear Dynamics in Quantum-Mechanical and Macroscopic Systems) [O] . Taniguchi Akira, Nagai Yuji, Natsume Yuhei 2005

机译：非绝热跃迁对质子动力学的影响（4）分子科学和核理论中的量子混沌和半经典理论，量子力学和宏观系统中的混沌和非线性动力学）

Importance of Anharmonicity,Recrossing Effects,and Quantum Mechanical Tunneling in Transition State Theory with Semiclassical Tunneling.A Test Case:The H_2+Cl Hydrogen Abstraction Reaction

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