Estimation of Solvation Entropy and Enthalpy via Analysis of Water Oxygen–Hydrogen Correlations

• Published in: Journal of chemical theory and computation Vol. 11; no. 11; pp. 5090 - 5102
• Main Authors: Velez-Vega, Camilo, McKay, Daniel J. J, Kurtzman, Tom, Aravamuthan, Vibhas, Pearlstein, Robert A, Duca, José S
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10.11.2015
• Subjects: Algorithms; Assessments; Computation; Correlation analysis; Design analysis; Enthalpy; Entropy; Hydrogen - chemistry; Molecular Dynamics Simulation; Oxygen - chemistry; Solvation; Solvents - chemistry; Thermodynamics; Water - chemistry
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.5b00439

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’s ability to enable detailed elucidation of solvation thermodynamic structures, which can provide valuable knowledge toward molecular design.