Understanding the physics of hydrophobic solvation

Mary K Coe, Robert Evans, Nigel B Wilding*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

8 Citations (Scopus)

Abstract

Simulations of water near extended hydrophobic spherical solutes have revealed the presence of a region of depleted density and accompanying enhanced density fluctuations.The physical origin of both phenomena has remained somewhat obscure. We investigate these effects employing a mesoscopic binding potential analysis, classical density functional theory (DFT) calculations for a simple Lennard-Jones (LJ) solvent and Grand Canonical Monte Carlo (GCMC) simulations of a monatomic water (mw) model. We argue that the density depletion and enhanced fluctuations are near-critical phenomena. Specifically, we show that they can be viewed as remnants of the critical drying surface phase transition that occurs at bulk liquid-vapor coexistence in the macroscopic planar limit, i.e.~as the solute radius $R_s\to\infty$. Focusing on the radial density profile $\rho(r)$ and a sensitive spatial measure of fluctuations, the local compressibility profile $\chi(r)$, our binding potential analysis provides explicit predictions for the manner in which the key features of $\rho(r)$ and $\chi(r)$ scale with $R_s$, the strength of solute-water attraction $\varepsilon_{sf}$, and the deviation from liquid-vapor coexistence of the chemical potential, $\delta\mu$. These scaling predictions are confirmed by our DFT calculations and GCMC simulations. As such our theory provides a firm basis for understanding the physics of hydrophobic solvation.
Original languageEnglish
Article number034508
JournalThe Journal of Chemical Physics
Volume158
Issue number3
DOIs
Publication statusPublished - 19 Jan 2023

Bibliographical note

Funding Information:
This work used the facilities of the Advanced Computing Research Centre, University of Bristol. We thank F. Turci for valuable discussions. R.E. acknowledges the support received under Leverhulme Trust Grant No. EM-2020-029\4.

Publisher Copyright:
© 2023 Author(s).

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