Single particle force distributions in simple fluids

Abstract

The distribution function, W(F), of the magnitude of the net force, F, on particles in simple fluids is considered, which follows on from our previous publication [A. C. Brańka, D. M. Heyes, and G. Rickayzen, J. Chem. Phys. 135, 164507 (2011)] concerning the pair force, f, distribution function, P(f), which is expressible in terms of the radial distribution function. We begin by discussing the force on an impurity particle in an otherwise pure fluid but later specialize to the pure fluid, which is studied in more detail. An approximate formula, expected to be valid asymptotically, for W(F) referred to as, W(1)(F) is derived by taking into account only binary spatial correlations in the fluid. It is found that W(1)(F) = P(f). Molecular dynamics simulations of W for the inverse power (IP) and Lennard-Jones potential fluids show that, as expected, W(F) and P(f) agree well in the large force limit for a wide range of densities and potential forms. The force at which the maximum in W(F) occurs for the IP fluids follows a different algebraic dependence with density in low and high density domains of the equilibrium fluid. Other characteristic features in the force distribution functions also exhibit the same trends. An exact formula is derived relating W(F) to P(x)(F(x)), the distribution function of the x-cartesian components of the net force, F(x), on a particle. W(F) and P(x)(F(x)) have the same analytical forms (apart from constants) in the low and high force limits.