Potential Energy Landscape of the Apparent First-Order Phase Transition between Low-Density and High-Density Amorphous Ice

TL;DR

This study uses the potential energy landscape formalism and computer simulations to analyze the sharp pressure-induced transformations between low-density and high-density amorphous ice, suggesting a first-order phase transition.

Contribution

It demonstrates that LDA and HDA occupy distinct megabasins in the PEL, and that their transformations resemble first-order phase transitions, providing new insights into amorphous ice behavior.

Findings

LDA and HDA are associated with separate megabasins in the PEL.

LDA-HDA transformation resembles a first-order phase transition.

Similar PEL behavior observed in liquid-to-ice-VII transition.

Abstract

The potential energy landscape (PEL) formalism is a valuable approach within statistical mechanics for describing supercooled liquids and glasses. Here we use the PEL formalism and computer simulations to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) at different temperatures. We employ the ST2 water model for which the LDA-HDA transformations are remarkably sharp, similar to what is observed in experiments, and reminiscent of a first-order phase transition. Our results are consistent with the view that LDA and HDA configurations are associated with two distinct regions (megabasins) of the PEL that are separated by a potential energy barrier. At higher temperature, we find that low-density liquid (LDL) configurations are located in the same megabasin as LDA, and that high-density liquid (HDL) configurations are located in the same megabasin as HDA. We show that the pressure-induced LDL-HDL and LDA-HDA transformations occur along paths that interconnect these two megabasins, but that the path followed by the liquid is different than the path followed by the amorphous solid. At higher pressure, we also study the liquid-to-ice-VII first-order phase transition, and find that the behavior of the PEL properties across this transition are qualitatively similar to the changes found during the LDA-HDA transformation. This similarity supports the interpretation that the LDA-HDA transformation is a first-order-like phase transition between out-of-equilibrium states.