“Direct” and “Correct” Calculation of Canonical and Microcanonical Rate Constants for Chemical Reactions
“Direct” and “Correct” Calculation of Canonical and Microcanonical Rate Constants for Chemical Reactions
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“直接”和“正确”计算化学反应的规范和微规范速率常数
DOI：
10.1021/jp973208o
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发表时间：
1998
影响因子：
2.9
通讯作者：
W. Miller
中科院分区：
文献类型：
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作者：
W. Miller
本文叙述了计算化学反应速率常数的理论方法，无论是给定总能量k（E）的微正则速率，还是给定温度k（T）的正则速率，都是“直接的”，即，绕过了必须解决完整的状态到状态量子反应散射问题的必要性，而且还“正确”，即，原则上精确（给定势能面，假设非相对论量子力学等）各种反应的应用，以说明各种动态情况下，例如，类似过渡态理论的动力学，其中系统直接通过相互作用（过渡态）区域和反应移动，形成长寿命的碰撞复合物。它也表明如何这个严格的量子理论可以与林德曼机制相结合，用于描述与浴气体碰撞的影响，以便能够治疗重组反应和其他影响的压力。最后，有几种方法.
Theoretical approaches for calculating rate constants of chemical reactionseither the microcanonical rate for a given total energy k(E) or the canonical rate for a given temperature k(T)are described that are both “direct”, i.e., bypass the necessity of having to solve the complete state-to-state quantum reactive scattering problem, yet also “correct”, i.e., in principle exact (given a potential energy surface, assuming nonrelativistic quantum mechanics, etc.) Applications to a variety of reactions are presented to illustrate the methodology for various dynamical situations, e.g., transition-state-theory-like dynamics where the system moves directly through the interaction (transition-state) region and reactions that form long-lived collision complexes. It is also shown how this rigorous quantum theory can be combined with the Lindemann mechanism for describing the effects of collisions with a bath gas, so as to be able to treat recombination reactions and other effects of pressure. Finally, several ways ...