Combining rare events techniques: phase change in Si nanoparticles

TL;DR

This paper presents a combined simulation approach to study phase stability in silicon nanoparticles, revealing size-dependent phase transitions between amorphous and crystalline states as temperature varies.

Contribution

It introduces a novel combined Restrained MD/Parallel Tempering method to analyze free energy differences in nanoparticle phase behavior.

Findings

Small nanoparticles are amorphous at low T and crystallize at higher T.

Large nanoparticles exhibit bulk-like behavior: crystalline at low T, amorphous at high T.

Phase transition temperatures depend on nanoparticle size.

Abstract

We introduce a combined Restrained MD/Parallel Tempering approach to study the difference in free energy as a function of a set of collective variables between two states in presence of unknown slow degrees of freedom. We applied this method to study the relative stability of the amorphous vs crystalline nanoparticles of size ranging between 0.8 and 1.8 nm as a function of the temperature. We found that, at variance with bulk systems, at low T small nanoparticles are amorphous and undergo an amorphous-to-crystalline phase transition at higher T. On the contrary, large nanoparticles recover the bulk-like behavior: crystalline at low $T$ and amorphous at high T.