Collective Variables for Crystallization Simulations -- from Early Developments to Recent Advances

TL;DR

This review discusses the development and application of collective variables in enhanced sampling simulations to better understand the microscopic processes of crystallization, highlighting recent advances and future challenges.

Contribution

It provides a comprehensive overview of the types and evolution of collective variables used in crystallization studies through enhanced sampling methods.

Findings

Categorization of CVs into four main types.

Discussion of the evolution of CVs over time.

Identification of current challenges and future directions.

Abstract

Crystallization is one of the most important physicochemical processes which has relevance in material science, biology, and the environment. Decades of experimental and theoretical efforts have been made to understand this fundamental symmetry-breaking transition. While experiments provide equilibrium structures and shapes of crystals, they are limited to unraveling how molecules aggregate to form crystal nuclei that subsequently transform into bulk crystals. Computer simulations, mainly molecular dynamics (MD), can provide such microscopic details during the early stage of a crystallization event. Crystallization is a rare event that takes place in timescales much longer than a typical equilibrium MD simulation can sample. This inadequate sampling of the MD method can be easily circumvented by the use of enhanced sampling (ES) simulations. An ES method enhances the fluctuations of a system's slow degrees of freedom, called collective variables (CVs), by applying a bias potential, and thereby transforms the system from one state to the other within a short timescale. The most crucial part of an ES method is to find suitable CVs which often needs intuition and several trial-and-error optimization steps. Over the years, a plethora of CVs has been developed and applied in the study of crystallization. In this review, we provide a brief overview of CVs that have been developed and used in ES simulations to study crystallization from melt or solution. These CVs can be categorized mainly into four types: (i) spherical particle-based, (ii) molecular template-based, (iii) physical property-based, and (iv) CVs obtained from dimensionality reduction techniques. We present the context-based evolution of CVs, discuss the current challenges, and propose future directions to further develop effective CVs for the study of crystallization of complex systems.