Understanding the physics of hydrophobic solvation (2212.04967v1)

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.