Size and shape dependence of finite-volume Kirkwood-Buff integrals.

Abstract

Analytic relations are derived for finite-volume integrals over the pair correlation function of a fluid, the 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 an 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, an 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.