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首页> 外文期刊>The Journal of Chemical Physics >NONEQUILIBRIUM SOLVENT EFFECTS ON THE S(N)2 REACTION USING A SELF-CONSISTENT REACTION FIELD CONTINUUM MODEL BASED ON MULTIPOLE EXPANSIONS
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NONEQUILIBRIUM SOLVENT EFFECTS ON THE S(N)2 REACTION USING A SELF-CONSISTENT REACTION FIELD CONTINUUM MODEL BASED ON MULTIPOLE EXPANSIONS

机译：基于多极点膨胀的自洽反应场连续模型对S（N）2反应的非平衡溶剂效应

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摘要

A simple model has been developed that allows analysis of nonequilibrium solvent effects on chemical processes. It is based on the use of a self-consistent reaction field approach using a multipole development of the solvation energy and on the separation of the inertial and noninertial polarization of the solvent. The solute's wave function is computed at the ab initio level. The main advantage with respect to previously reported models is that the inclusion of nonequilibrium or dynamic solvent effects are introduced through the definition of 3. single solvent coordinate which is related to the chemical system coordinates. Besides, inclusion of polarization effects is straightforward. Results are presented for the S(N)2 reaction F-+CH3F-->FCH3+F-. The frozen-solvent hypothesis and the role of solvent fluctuations are discussed. It is shown that the climb to the transition barrier must be preceded by a convenient fluctuation of the solvent so that its inertial polarization component is suitable to solvate the transition state. Other solvent fluctuations, energetically less favorable, could decrease or even suppress the transition barrier. Nonequilibrium solvation effects on the value of the transmission coefficient are discussed. The methodology proposed in this work may be extended to the study of other rapid processes in solution such as proton transfers or electronic excitations. (C) 1995 American Institute of Physics. [References: 77]
机译：已经开发了一个简单的模型，可以分析非平衡溶剂对化学过程的影响。它基于使用溶剂化能量的多极展开的自洽反应场方法，以及溶剂的惯性和非惯性极化的分离。溶质的波动函数是从头计算的。关于先前报告的模型的主要优点是，通过定义3.与化学体系坐标相关的单一溶剂坐标，引入了非平衡或动态溶剂效应。此外，包含极化效应很简单。给出了S（N）2反应F- + CH3F-> FCH3 + F-的结果。讨论了冷冻溶剂假说和溶剂波动的作用。结果表明，在跃迁至过渡势垒之前必须先进行溶剂的方便波动，以使其惯性极化分量适合于溶剂化过渡态。能量上较不利的其他溶剂波动可能会降低甚至抑制过渡势垒。讨论了非平衡溶剂化对透射系数值的影响。这项工作中提出的方法可以扩展到溶液中其他快速过程的研究，例如质子转移或电子激发。 （C）1995年美国物理研究所。 [参考：77]

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