Local measures of fluctuations in inhomogeneous liquids: statistical mechanics and illustrative applications

Abstract

Abstract We show in detail how three one-body fluctuation profiles, namely the local compressibility, the local thermal susceptibility, and the reduced density, can be obtained from a statistical mechanical many-body description of classical particle-based systems. We present several different and equivalent routes to the definition of each fluctuation profile, facilitating their explicit numerical calculation in inhomogeneous equilibrium systems. This underlying framework is used for the derivation of further properties such as hard wall contact theorems and novel types of inhomogeneous one-body Ornstein–Zernike equations. The practical accessibility of all three fluctuation profiles is exemplified by grand canonical Monte Carlo simulations that we present for hard sphere, Gaussian core and Lennard–Jones fluids in confinement.