Effects of confinement on the thermodynamics of supercooled water

Abstract

The main focus of this thesis is to understand how confinement alters the phase diagram of supercooled liquid water by employing methods of statistical mechanics and numerical simulations. Water is very complex and anomalous when compared to simple liquids. For example, experimental data for liquid water reveals the presence of a temperature of maximum density (TMD) below which the density decreases under isobaric cooling. Another anomaly is the hypothesized liquid- liquid phase transition (LLPT) between two types of liquid water with different densities. In this thesis we study how confinement affects such anomalies as TMD and LLPT in supercooled liquid water. This thesis is separated into three parts: (i) Monte Carlo simulations of a 2D coarsegrained model of a water layer confined in a fixed disordered matrix of hydrophobic nanoparticles, (ii) molecular dynamics simulations of a Jagla ramp model of liquid confined in fixed ordered and disordered matrices of hydrophobic nanoparticles, and (iii ) all-atom simulations of trehalose and maltose in aqueous solut ion of lysozyme. In Part (i), we perform Monte Carlo simulations and find that a nanoparticle concentration as small as 2.4% is enough to destroy the LLPT for pressure P > 0.14 GPa. Moreover, we find a substantial (more t han 90%) decrease of compressibility, t hermal expansion coefficient and specific heat at high P and low temperature T upon increase of nanoparticle concentration from 0% to 25%. In Part (ii), we ask how, for single component systems interacting via a soft-core isotropic potential with two characteristic length scales, t he geometry of hydrophobic confinement affects the phase diagram. We use molecular dynamics simulations to study particles interacting through a ramp potential and a shoulder potential, each confined in a fixed matrix of nanoscopic particles with a fixed volume fraction. We find a substantial weakening of the LLPT and the disappearance of TMD upon the increase of disorder in the confining geometry. In Part (iii), we study aqueous systems with all-atom simulations. We are currently investigating the mechanism of water-trehalose-protein and water-maltose-protein interaction upon supercooling for its relevance to bioprotection.