Entropy, diffusivity and the energy landscape of a water-like fluid

TL;DR

This study uses molecular dynamics and INM analysis to explore how thermodynamics, transport, and energy landscape features relate in a water-like fluid with anomalies, revealing key insights into entropy contributions and diffusivity scaling.

Contribution

It demonstrates Rosenfeld-scaling in a water-like model and links INM spectral features to anomalous transport and entropy behavior, providing new understanding of the energy landscape.

Findings

Rosenfeld-scaling applies to this water-like fluid model.

INM spectra reveal bimodal frequency distributions linked to anomalies.

Imaginary mode entropy captures non-monotonic behavior of excess entropy.

Abstract

Molecular dynamics simulations and instantaneous normal mode (INM) analysis of a fluid with core-softened pair interactions and water-like liquid-state anomalies are performed to obtain an understanding of the relationship between thermodynamics, transport properties and the poten- tial energy landscape. Rosenfeld-scaling of diffusivities with the thermodynamic excess and pair correlation entropy is demonstrated for this model. The INM spectra are shown to carry infor- mation about the dynamical consequences of the interplay between length scales characteristic of anomalous fluids, such as bimodality of the real and imaginary branches of the frequency distribu- tion. The INM spectral information is used to partition the liquid entropy into two contributions associated with the real and imaginary frequency modes; only the entropy contribution from the imaginary branch captures the non-monotonic behaviour of the excess entropy and diffusivity in the anomalous regime of the fluid.