Waterlike anomalies in hard core-soft shell nanoparticles using a effective potential approach: pinned vs adsorbed polymers

TL;DR

This study uses simulations to explore phase behavior and waterlike anomalies in polymer-grafted nanoparticles with different polymer orientations, revealing how fixed or free polymers influence anomalies and morphologies.

Contribution

It introduces effective core-softened potentials for nanoparticle systems with fixed and free polymers, analyzing their phase diagrams and anomalies through large-scale simulations.

Findings

Waterlike density and diffusion anomalies observed

Different morphologies such as stripes and honeycomb identified

Anomalies linked to potential length scale competition in fixed polymers case

Abstract

In this work, a two dimensional system of polymer grafted nanoparticles is analyzed using large-scale Langevin Dymanics simulations. Effective core-softened potentials were obtained for two cases: one where the polymers are free to rotate around the nanoparticle core and a second where the polymers are fixed, with a $45^\circ$ angle between them. The use of effective core-softened potentials allow us to explore the complete system phase space. In this way, the $PT$, $T\rho$ and $P\rho$ phase diagrams for each potential were obtained, with all fluid and solid phases. The phase boundaries were defined analyzing the specific heat at constant pressure, the system mean square displacement, the radial distribution function and the discontinuities in the density-pressure phase diagram. Also, due the competition in the system we have observed the presence of waterlike anomalies, such as the temperature of maximum density - in addition with a tendency of the TMD to move to lower temperatures (negative slope)- and the diffusion anomaly. It was observed different morphologies (stripes, honeycomb, amorphous) for each nanoparticle. We observed that for the fixed polymers case the waterlike anomalies are originated by the competition between the potential characteristic length scales, while for the free to rotate case the anomalies arises due a smaller region of stability in the phase diagram and no competition between the scales was observed.