Ostwald's Rule of Stages in One-Dimension

TL;DR

This study investigates Ostwald's Rule of Stages in one-dimensional peptide assemblies on graphite, revealing that phase evolution is driven by kinetics and boundary fluctuations, providing insights into 2D phase transformations.

Contribution

It demonstrates that Ostwald's Rule applies in one-dimensional systems due to kinetic factors, not thermodynamic stability, expanding understanding of phase transformations in low-dimensional assemblies.

Findings

Phase evolution follows Ostwald's Rule for kinetic reasons.

Stable phase replaces metastable via dissolution-reprecipitation.

Boundary fluctuations enable phase transformation mechanisms.

Abstract

Ostwald's Rule of Stages, which is one of the most widely observed phenomena associated with crystallization of polymorphs, follows naturally from the thermodynamics of nucleation. However, most observations of its manifestations have been limited to three-dimensional crystals and its validity in one-dimension, where no nucleation barrier exists, remains unclear. Here we investigate the two-dimensional assemblies and phase transformation mechanisms of a peptide that forms two distinct phases on graphite via one-dimensional nucleation using in situ atomic force microscopy. We find that the evolution of phases illustrates Ostwald's Rule, but does so for purely kinetic reasons, and that the stable phase replaces the metastable via a dissolution-reprecipitation mechanism enabled by inherent fluctuations of the phase boundary. The findings provide general insights into the growth and transformation mechanisms of coexisting two-dimensional phases and thus delineate a strategy for capturing transient two-dimensional structures.