Nanoparticle Confinement in Anomalous Liquids

Abstract

We investigate using molecular dynamics the effect of the structure of nanoconfinement for liquids with water-like anomalies and liquid-liquid phase transition (LLPT). We find that if the confinement is in an ordered matrix of nanoparticles (NPs) the anomalies are preserved, although the LLPT shifts to lower temperatures, higher pressures and higher densities with respect to bulk. On the contrary, if the NPs matrix is disordered, we find a drastically different phase diagram: the LLPT occurs only in a reduced interval of densities and the anomalies are washed out. To understand this effect we calculate the changes in the system at the microscopic level. In all the different confinements considered here we observe a dramatic increase of density of liquid near the confining NPs. In the disordered case the confinement induces larger heterogeneity in the local density, responsible for the weakening of the LLPT and the disappearance of anomalies.