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Role of local structure on motions on the potential energy landscape for a model supercooled polymer

J. Chem. Phys. 122, 174515 (2005); doi:10.1063/1.1888505

Published 5 May 2005

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Tushar S. Jain and Juan J. de Pablo
Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706
We have conducted detailed Monte Carlo and molecular dynamics simulations of a model glass forming polymeric system near its apparent glass transition temperature. We have characterized the local structure of the glass using a Voronoi–Delaunay analysis of local particle arrangements. After a perturbative face elimination, we find that a significant fraction of Voronoi polyhedra consist of 12 pentagonal faces, a sign of icosahedral ordering. Further, we have identified metabasins of particle vibrations on the potential energy landscape on the basis of persistence of particle positions and neighbors over a simulated trajectory. We find that the residence times for vibrations are correlated with a particular Voronoi volume and number of neighbors of a particle; the largest metabasins correspond to particles whose average Voronoi volume is close to the value expected on the basis of the density, and whose approximate number of neighbors is close to 12. The local distortion around a particle, measured in terms of the tetrahedricity of the Delaunay simplices, reveals that the particles with a higher degree of local distortion are likely to transition faster to a neighboring metabasin. In addition to the transition between metabasins, we have also examined the influence of vibrations at inherent structures (IS) on the local structure, and find that the the low frequency modes at the IS exhibit the greatest curvature with respect to the local structure. We believe that these results establish an important connection between the local structure of glass formers and the activated dynamics, thereby providing insights into the origins of dynamic heterogeneities. ©2005 American Institute of Physics
History: Received 27 August 2004; accepted 16 February 2005; published 5 May 2005
Permalink: http://link.aip.org/link/?JCPSA6/122/174515/1
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KEYWORDS and PACS

Keywords
PACS
  • 61.43.Bn
    Structural modeling of disordered solids including serial-addition models, computer simulation
  • 64.70.Pf
    Glass transitions
  • 61.43.Fs
    Structure of glasses
  • 63.50.+x
    Vibrational states in disordered systems
  • YEAR: 2005

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

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