Issue 10, 2024

Enthalpies and entropies of hydration from Monte Carlo simulations

Abstract

The changes in free energy, enthalpy, and entropy for transfer of a solute from the gas phase into solution are the fundamental thermodynamic quantities that characterize the solvation process. Owing to the development of methods based on free-energy perturbation theory, computation of free energies of solvation has become routine in conjunction with Monte Carlo (MC) statistical mechanics and molecular dynamics (MD) simulations. Computation of the enthalpy change and by inference the entropy change is more challenging. Two methods are considered in this work corresponding to direct averaging for the solvent and solution and to computing the temperature derivative of the free energy in the van’t Hoff approach. The application is for neutral organic solutes in TIP4P water using long MC simulations to improve precision. Definitive results are also provided for pure TIP4P water. While the uncertainty in computed free energies of hydration is ca. 0.05 kcal mol−1, it is ca. 0.4 kcal mol−1 for the enthalpy changes from either van’t Hoff plots or the direct method with sampling for 5 billion MC configurations. Partial molar volumes of hydration are also computed by the direct method; they agree well with experimental data with an average deviation of 3 cm3 mol−1. In addition, the results permit breakdown of the errors in the free energy changes from the OPLS-AA force field into their enthalpic and entropic components. The excess hydrophobicity of organic solutes is enthalpic in origin.

Graphical abstract: Enthalpies and entropies of hydration from Monte Carlo simulations

Article information

Article type
Paper
Submitted
22 Janv. 2024
Accepted
22 Febr. 2024
First published
23 Febr. 2024
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2024,26, 8141-8147

Enthalpies and entropies of hydration from Monte Carlo simulations

W. L. Jorgensen, Phys. Chem. Chem. Phys., 2024, 26, 8141 DOI: 10.1039/D4CP00297K

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