Nonequilibrium solvation dynamics in solution reactions
Nonequilibrium solvation dynamics in solution reactions
复制标题
溶液反应中的非平衡溶剂化动力学
DOI：
--
复制
发表时间：
1983
期刊：
影响因子：
--
通讯作者：
J. Hynes
中科院分区：
文献类型：
--
作者：
G. Zwan;J. Hynes
我们构建了描述非平衡溶剂化和溶剂参与溶液反应坐标的理论框架。反应偶极异构化模型说明了这一框架。我们证明了多维反应坐标图等价于一维描述，其中广义摩擦表征和量化了非平衡溶剂化对反应速率的影响。确定了平衡溶剂化和平均势思想正确的绝热状态。几种不同的非平衡溶剂化制度被识别和描述在分子术语。在有效质量体系中，平衡溶剂化思想正确地给出了反应势垒曲率，但溶剂惯性改变了势垒通过速率。在非绝热状态下，溶剂在障碍通道中被“冻结”，不能提供平衡溶剂化。在极化笼化体系中，反应物质与移动的溶剂相适应，而不是相反，溶剂在反应坐标中起重要作用。每一种体系中的速率常数都与反应动力学和溶剂动力学有关。
We construct a theoretical framework for the description of nonequilibrium solvation and solvent participation in the reaction coordinate for solution reactions. The framework is illustrated by a model of reactive dipole isomerization. We show that a multidimensional reaction coordinate picture is equivalent to a one dimensional description in which a generalized friction characterizes and quantifies nonequilibrium solvation effects on the reaction rate. The adiabatic regime where equilibrium solvation and mean potential ideas are correct is identified. Several distinct regimes of nonequilibrium solvation are identified and described in molecular terms. In the effective mass regime, equilibrium solvation ideas give the reaction barrier curvature correctly, but solvent inertia modifies the barrier passage rate. In the nonadiabatic regime, the solvent is ‘‘frozen’’ during the barrier passage and cannot provide equilibrium solvation. In the polarization caging regime, the reacting species adjust to the moving solvent, rather than vice versa, and the solvent is heavily involved in the reaction coordinate. The rate constant in each of these regimes is related to reactive and solvent dynamics.