Enhancing entropy and enthalpy fluctuations to drive crystallization in atomistic simulations

TL;DR

This paper introduces two collective variables based on entropy and enthalpy to enhance crystallization in atomistic simulations, enabling spontaneous and reversible phase transitions without biasing the crystal structure.

Contribution

It proposes a novel approach using enthalpic and entropic collective variables to drive and study crystallization in molecular simulations.

Findings

Successful demonstration with sodium and aluminum systems

Systems transform spontaneously between liquid and solid phases

Approach does not bias the resulting crystal structure

Abstract

Crystallization is a process of great practical relevance in which rare but crucial fluctuations lead to the formation of a solid phase starting from the liquid. Like in all first order first transitions there is an interplay between enthalpy and entropy. Based on this idea, to drive crystallization in molecular simulations, we introduce two collective variables, one enthalpic and the other entropic. Defined in this way, these collective variables do not prejudge the structure the system is going to crystallize into. We show the usefulness of this approach by studying the case of sodium and aluminum that crystallize in the bcc and fcc crystalline structure, respectively. Using these two generic collective variables, we perform variationally enhanced sampling and well tempered metadynamics simulations, and find that the systems transform spontaneously and reversibly between the liquid and the solid phases.