Ben-Amotz Dor, Raineri Fernando O, Stell George
Purdue University, Department of Chemistry, West Lafayette, Indiana 47907-1393, USA.
J Phys Chem B. 2005 Apr 14;109(14):6866-78. doi: 10.1021/jp045090z.
Potential distribution and coupling parameter theories are combined to interrelate previous solvation thermodynamic results and derive several new expressions for the solvent reorganization energy at both constant volume and constant pressure. We further demonstrate that the usual decomposition of the chemical potential into noncompensating energetic and entropic contributions may be extended to obtain a Gaussian fluctuation approximation for the chemical potential plus an exact cumulant expansion for the remainder. These exact expressions are further related to approximate first-order thermodynamic perturbation theory predictions and used to obtain a coupling-parameter integral expression for the sum of all higher-order terms in the perturbation series. The results are compared with the experimental global solvation thermodynamic functions for xenon dissolved in n-hexane and water (under ambient conditions). These comparisons imply that the constant-volume solvent reorganization energy has a magnitude of at most approximately kT in both experimental solutions. The results are used to extract numerical values of the solute-solvent mean interaction energy and associated fluctuation entropy directly from experimental solvation thermodynamic measurements.
将势分布理论和耦合参数理论相结合，以关联先前的溶剂化热力学结果，并推导出恒容和恒压下溶剂重组能的几个新表达式。我们进一步证明，通常将化学势分解为非补偿性的能量和熵贡献，可以扩展为获得化学势的高斯涨落近似以及其余部分的精确累积量展开。这些精确表达式进一步与近似的一阶热力学微扰理论预测相关，并用于获得微扰级数中所有高阶项之和的耦合参数积分表达式。将结果与氙溶解在正己烷和水中（在环境条件下）的实验全局溶剂化热力学函数进行比较。这些比较表明，在两种实验溶液中，恒容溶剂重组能的大小最多约为kT。结果用于直接从实验溶剂化热力学测量中提取溶质 - 溶剂平均相互作用能和相关涨落熵的数值。
