Self-diffusion coefficient of the hard-sphere fluid: System size dependence and empirical correlations

Heyes, D.M. and Cass, M.J. and Powles, J.G. and Evans, W.A.B. (2007) Self-diffusion coefficient of the hard-sphere fluid: System size dependence and empirical correlations. Journal of Physical Chemistry B, 111 (6). pp. 1455-1464. ISSN 1520-6106 . (The full text of this publication is not available from this repository)

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http://pubs.acs.org/cgi-bin/article.cgi/jpcbfk/200...

Abstract

Molecular dynamics simulations have been used to calculate the self-diffusion coefficient, D, of the hard sphere fluid over a wide density range and for different numbers of particles, N, between 32 and 10 976. These data are fitted to the relationship D = D-infinity - AN(-alpha) where the parameters D-infinity, A, and alpha are all density-dependent (the temperature dependence of D can be trivially scaled out in all cases). The value alpha = 1/3 has been predicted on the basis of hydrodynamic arguments. In the studied system size range, the best value of alpha is similar to 1/3 at intermediate packing fractions of similar to 0.35, but increases in the low- and high-density extremes. At high density, the scaling follows more closely that of the thermodynamic properties, that is, with an exponent of order unity. At low packing fractions (less than similar to 0.1), the exponent increases again, appearing to approach a limiting value of unity in the zero-density limit. The origin of this strong N dependence at low density probably lies in the divergence in the mean path between collisions, as compared with the dimensions of the simulation cell. A new simple analytical fit formula based on fitting to previous simulation data is proposed for the density dependence of the shear viscosity. The Stokes-Einstein relationship and the dependence of D on the excess entropy were also explored. The product D eta(p)(s) with p = 0.975 was found to be approximately constant, with a value of 0.15 in the packing fraction range between 0.2 and 0.5.

Item Type: Article
Subjects: Q Science > QC Physics
Divisions: Faculties > Science Technology and Medical Studies > School of Physical Sciences
Depositing User: Maureen Cook
Date Deposited: 18 Mar 2008 09:52
Last Modified: 14 Jan 2010 14:06
Resource URI: http://kar.kent.ac.uk/id/eprint/2209 (The current URI for this page, for reference purposes)
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