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We examine the attractive interaction between an excess electron and the dipole moments of polar molecules forming a cluster or a liquid. This interaction determines the size dependence of the electro...

The effect of solvation on the conformation of freely jointed repulsive trimers

J. Chem. Phys. 101, 6013 (1994); doi:10.1063/1.467316

Issue Date: 1 October 1994

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Christopher J. Grayce
Department of Materials Science, University of Illinois, Urbana, Illinois 61801

Juan J. de Pablo
Department of Chemical Engineering, University of Wisconsin, Madison, Wisconsin, 53706
The effect of solvation on the conformation of a dense one-component fluid composed of freely jointed repulsive trimers is calculated theoretically and compared to results from computer simulation. All monomers in the fluid interact with one another via the purely repulsive, shifted–truncated Lennard-Jones potential. We are able to confirm an earlier suggestion that when the conformation of nonpolar flexible molecules is calculated with a site–site solvation potential and the reference interaction site model (RISM) theory, better results are obtained with the recently derived Percus–Yevick (PY) style solvation potential than the hypernetted-chain (HNC) style or Gaussian-fluctuation solvation potential. Interestingly, although RISM-based theory predicts well the general shape of the probability distribution of trimer conformations, it cannot recover a small feature observed in the simulations and expected on simple physical grounds. At high density, there are three preferred conformations of the trimer, corresponding to the three ways in which a flexible trimer can be fitted into a dense fluid with locally hexagonally close-packed (hcp) symmetry. RISM-based theories predict a preference for only two conformations of the trimer. To predict the preference for all three conformations, information about three-site correlations in the fluid must be incorporated into the theory. We present a theory that includes this information and is thereby capable of reproducing the results of our simulations. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 18 March 1994; accepted 15 June 1994
Permalink: http://link.aip.org/link/?JCPSA6/101/6013/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.60.Lf
    Physical chemistry Chemical thermodynamics Thermodynamics of solutions
  • YEAR: 1994

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
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REFERENCES (45)
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