System Size Dependence of the Diffusion Coefficients in MD Simulations: A Simple Correction Formula for Pure Dense Fluids

Abstract

A practical correction formula relating the self-diffusion coefficient of dense liquids from molecular dynamics (MD) simulations with periodic boundary conditions to the self-diffusion coefficient in the thermodynamic limit is discussed. This formula applies to pure dense fluids and has a very simple form D = D 0 (1 – γ N –1/3 ), where D 0 is the self-diffusion coefficient in the thermodynamic limit and N is the number of particles in the simulation. The numerical factor γ is dependent on the geometry of the simulation cell. Remarkably, γ ≃ 1.0 is the most popular cubic geometry. The success of this formula is supported by results from MD simulations, including very recent simulations with a “magic” simulation geometry.

Topics & Concepts