On the local and nonlocal components of solvation thermodynamics and their relation to solvation shell models
On the local and nonlocal components of solvation thermodynamics and their relation to solvation shell models
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关于溶剂化热力学的局部和非局部分量及其与溶剂化壳模型的关系
DOI：
10.1063/1.477097
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发表时间：
1998
影响因子：
4.4
通讯作者：
R. Levy
中科院分区：
文献类型：
--
作者：
N. Matubayasi;Emilio Gallicchio;R. Levy
本文提出了一种确定局部和非局部过量偏摩尔量的方法。这个过程是基于对多余的热力学量的分析，表示为系统体积的局部估计的积分。局部组分可用溶剂化壳模型描述，与溶质插入条件无关。的非局部组件有关的渐近行为的分布函数在大距离的溶质，他们引起的系综依赖的溶剂化的热力学量。结果表明，在恒压过程中，通过使用自然选择的本地估计，多余的偏摩尔能量，焓，熵，和体积的非本地组件是不存在的。我们的分析和一个唯象模型，表示过剩的热力学量的溶质体积，表面积和直径之间的关系也被认为是和有效性的…
A procedure for identifying the local and nonlocal components of excess partial molar quantities is presented. This procedure is based on an analysis of the excess thermodynamic quantities expressed as integrals of local estimators over the system volume. The local components can be described in terms of the solvation shell model and are independent of the condition of solute insertion. The nonlocal components are related to the asymptotic behavior of distribution functions at large distances from the solute and they give rise to the ensemble dependence of the thermodynamic quantities of solvation. It is shown that in the constant pressure process, by using natural choices for the local estimators, the nonlocal components of the excess partial molar energy, enthalpy, entropy, and volume are absent. The relationship between our analysis and a phenomenological model which expresses excess thermodynamic quantities in terms of the solute volume, surface area, and diameter is also considered and the validity o...