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Dynamics of a molecular glass former: Energy landscapes for diffusion in ortho-terphenyl.

Accepted version
Peer-reviewed

Type

Article

Change log

Authors

Niblett, SP 
de Souza, VK 
Stevenson, JD 
Wales, DJ 

Abstract

Relaxation times and transport processes of many glass-forming supercooled liquids exhibit a super-Arrhenius temperature dependence. We examine this phenomenon by computer simulation of the Lewis-Wahnström model for ortho-terphenyl. We propose a microscopic definition for a single-molecule cage-breaking transition and show that, when correlation behaviour is taken into account, these rearrangements are sufficient to reproduce the correct translational diffusion constants over an intermediate temperature range in the supercooled regime. We show that super-Arrhenius behaviour can be attributed to increasing negative correlation in particle movement at lower temperatures and relate this to the cage-breaking description. Finally, we sample the potential energy landscape of the model and show that it displays hierarchical ordering. Substructures in the landscape, which may correspond to metabasins, have boundaries defined by cage-breaking transitions. The cage-breaking formulation provides a direct link between the potential energy landscape and macroscopic diffusion behaviour.

Description

Keywords

0306 Physical Chemistry (incl. Structural), Brain Disorders

Journal Title

J Chem Phys

Conference Name

Journal ISSN

0021-9606
1089-7690

Volume Title

145

Publisher

AIP Publishing
Sponsorship
This work was supported by the University of Cambridge through a CHSS studentship to S.P.N., and by the European Research Council.