Size and shape dependence of finite volume Kirkwood-Buff integrals

Abstract

Analytic relations are derived for finite volume integrals over the radial distribution function of a fluid, so-called Kirkwood-Buff integrals. Closed form expressions are obtained for cubes and cuboids, the system shapes commonly employed in molecular simulations. When finite volume Kirkwood-Buff integrals are expanded over inverse system size, the leading term depends on shape only through the surface area to volume ratio. This conjecture is proved for arbitrary shapes and a general expression for the leading term is derived. From this, a new extrapolation to the infinite volume limit is proposed, which converges much faster with system size than previous approximations and thus significantly simplifies the numerical computations.