Calculations of hydration entropies of hydrophobic, polar, and ionic solutes in the framework of the Langevin dipoles solvation model
Calculations of hydration entropies of hydrophobic, polar, and ionic solutes in the framework of the Langevin dipoles solvation model
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DOI：
10.1021/jp992041r
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发表时间：
1999-11-18
影响因子：
3.3
通讯作者：
Warshel, A
中科院分区：
文献类型：
--
作者：
Florián, J;Warshel, A
一个朗之万偶极溶剂化模型，可以确定从气相到水溶液的分子转移的熵的开发和检查。这种计算方法涉及使用溶质的电位依赖性表面积的水化熵的疏水部分的计算。这一贡献是增强的固定熵项，占附近的任意形状的带电溶质的溶剂偶极子的顺序。熵贡献的水化自由能的55个中性和70个离子溶质在298 K的计算使用所提出的算法和结果进行了比较，现有的实验数据。此外，它表明，水化熵显着贡献的总活化和反应熵的质子转移和亲核取代反应。
A Langevin dipoles solvation model that can determine the entropies of transfer of molecules from the gas phase to aqueous solution is developed and examined. This computational approach involves the calculation of the hydrophobic part of the hydration entropy using the potential-dependent surface area of the solute. This contribution is augmented by an immobilization entropy term that accounts for the ordering of the solvent dipoles near charged solutes of arbitrary shape. The entropic contributions to the hydration free energies of 55 neutral and 70 ionic solutes at 298 K are calculated using the proposed algorithm and the results are compared to the available experimental data. In addition, it is shown that the hydration entropy contributes significantly to the total activation and reaction entropies of proton transfer and nucleophilic substitution reactions.