Inclusion of nonequilibrium continuum solvation effects in variational transition state theory
Inclusion of nonequilibrium continuum solvation effects in variational transition state theory
复制标题
将非平衡连续溶剂化效应纳入变分过渡态理论
DOI：
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发表时间：
1993
期刊：
影响因子：
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通讯作者：
B. Garrett
中科院分区：
文献类型：
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作者：
D. Truhlar;G. Schenter;B. Garrett
我们为溶液中的反应定义了一组通用的有效溶剂坐标，这应该特别适合于极性溶剂。对于电荷随沿反应坐标的运动或与反应坐标垂直的运动的变化，没有假定特定的泛函形式，因此，该形式允许使用溶质电荷分布的电子结构计算来处理任意反应类型。该理论的一个关键假设是，非平衡极化场可以用线性几何位移产生的绝热极化场来表示。所得结果与笛卡尔坐标正则变分过渡态理论相结合，提供了一种在实际计算速率常数时同时考虑非耗散连续介质溶剂的平衡和非平衡溶剂化效应的一般方法。
We define a general set of effective solvent coordinates for reactions in solution that should be especially well suited for polar solvents. No specific functional form is assumed for the variation of charges with motions along or orthogonal to the reaction coordinate, and as a consequence the formalism allows the treatment of arbitrary reaction types using electronic structure calculations for the solute charge distribution. A critical assumption of the theory is that the nonequilibrium polarization field may be represented in terms of the adiabatic polarization fields that arise for linear geometric displacements. The results are combined with the Cartesian‐coordinate canonical variational transition state theory presented previously to provide a general method for including both equilibrium and nonequilibrium solvation effects of a nondissipative, continuum‐dielectric solvent in practical calculations of rate constants.