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Article
Solid−Fluid and Solid−Solid Equilibrium in Hard Sphere United Atom Models of n-Alkanes: Rotator Phase Stability
Journal of Physical Chemistry B (2009)
  • Peter A Monson, University of Massachusetts - Amherst
  • M. Cao
Abstract
We present a study of the phase behavior for models of n-alkanes with chain lengths up to C21 based on hard sphere united atom models of methyl and methylene groups, with fixed bond lengths and C−C−C bond angles. We extend earlier work on such models of shorter alkanes by allowing for gauche conformations in the chains. We focus particularly on the orientational order about the chain axes in the solid phase near the melting point, and our model shows how the loss of this orientational order leads to the formation of rotator phases. We have made extensive calculations of the thermodynamic properties of the models as well as order parameters for tracking the degree of orientational order around the chain axis. Depending on the chain length and whether the carbon number is even or odd, the model exhibits both a rotator phase and a more orientationally ordered solid phase in addition to the fluid phase. Our results indicate that the transition between the two solid phases is first-order with a small density change. The results are qualitatively similar to those seen experimentally and show that rotator phases can appear in models of alkanes without explicit treatment of attractive forces or explicit treatment of the hydrogen atoms in the chains.
Disciplines
Publication Date
2009
Publisher Statement
DOI: 10.1021/jp902887w Copyright 2009 by The American Chemical Society
Citation Information
Peter A Monson and M. Cao. "Solid−Fluid and Solid−Solid Equilibrium in Hard Sphere United Atom Models of n-Alkanes: Rotator Phase Stability" Journal of Physical Chemistry B Vol. 113 Iss. 42 (2009)
Available at: http://works.bepress.com/peter_monson/9/