Self-diffusion coefficient of the hard-sphere fluid: system size dependence and empirical correlations.
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 approximately 1/3 at intermediate packing fractions of approximately 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 approximately 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 Deta(s)p 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.
Heyes
D M
DM
Division of Chemistry, School of Biomedical and Molecular Sciences, University of Surrey, Guildford GU2 7XH, UK. d.heyes@surrey.ac.uk
Cass
M J
MJ
Powles
J G
JG
Evans
W A B
WA
D000465:Algorithms; D003198:Computer Simulation; D004058:Diffusion; D006244:Hardness; D016018:Least-Squares Analysis; D044085:Microfluidics; D008968:Molecular Conformation; D053758:Nanoparticles / Q000737:chemistry*; D010316:Particle Size; D014783:Viscosity