The potential energy landscape for crystallisation of a Lennard-Jones fluid

Vanessa K De Souza,David J Wales

doi:10.1088/1742-5468/2016/07/074001

Vanessa K De Souza, David J Wales

Open Access

https://doi.org/10.1088/1742-5468/2016/07/074001

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Abstract

Crystallisation pathways are explored by direct analysis of the potential energy landscape for a system of Lennard-Jones particles with periodic boundary conditions. A database of minima and transition states linking liquid and crystalline states is constructed using discrete path sampling and the entire potential energy landscape from liquid to crystal is visualised. We demonstrate that there is a strong negative correlation between the number of atoms in the largest crystalline cluster and the potential energy. In common with previous results we find a strong bias towards the growth of FCC rather than HCP clusters, despite a very small potential energy difference. We characterise three types of perfect crystals with very similar energies: pure FCC, pure HCP, and combinations of FCC and HCP layers. There are also many slightly defective crystalline structures. The effect of the simulation box is analysed for a supercell containing 864 atoms. There are low barriers between some of the different crystalline structures via pathways involving sliding layers, and many different defective structures with FCC layers stacked at an angle to the periodic box. Finally, we compare a binary Lennard-Jones system and visualise the potential energy landscape from supercooled liquid to crystal.

Highlights

ContentsCrystallisation is the formation of an ordered solid from a disordered liquid
We will describe the energy landscape obtained from discrete path sampling for the 864-atom Lennard-Jones supercell defined above
Having found an initial path between the liquid and crystalline states we explored the landscape in the crystal/nucleation region around it

Summary

Introduction

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