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

Published version
Peer-reviewed

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Authors

De Souza, VK 
Wales, DJ 

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.

Description

Keywords

energy landscapes (theory)

Journal Title

Journal of Statistical Mechanics: Theory and Experiment

Conference Name

Journal ISSN

1742-5468
1742-5468

Volume Title

2016

Publisher

IOP Publishing
Sponsorship
Engineering and Physical Sciences Research Council (EP/I001352/1)
We acknowledge the Engineering and Physical Sciences Research Council, UK (EPSRC) for funding under Programme Grant EP/I001352/1 ... VKD is grateful to Darwin College, Cambridge for a Research Fellowship.