Estimation of Solvation Entropy and Enthalpy via Analysis of Water Oxygen鈥揌ydrogen Correlations

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• 作者：Camilo Velez-Vega ; Daniel J. J. McKay ; Tom Kurtzman ; Vibhas Aravamuthan ; Robert A. Pearlstein ; Jos茅 S. Duca
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2015
• 出版时间：November 10, 2015
• 年：2015
• 卷：11
• 期：11
• 页码：5090-5102
• 全文大小：549K
• ISSN：1549-9626

文摘

A statistical-mechanical framework for estimation of solvation entropies and enthalpies is proposed, which is based on the analysis of water as a mixture of correlated water oxygens and water hydrogens. Entropic contributions of increasing order are cast in terms of a Mutual Information Expansion that is evaluated to pairwise interactions. In turn, the enthalpy is computed directly from a distance-based hydrogen bonding energy algorithm. The resulting expressions are employed for grid-based analyses of Molecular Dynamics simulations. In this first assessment of the methodology, we obtained global estimates of the excess entropy and enthalpy of water that are in good agreement with experiment and examined the method鈥檚 ability to enable detailed elucidation of solvation thermodynamic structures, which can provide valuable knowledge toward molecular design.