Equations Governing the Statistical Mechanical Distribution Functions of a Molecular Fluid Interacting with a Solid Boundary

Abstract

An infinite set of integrodifferential equations, governing the equilibrium, statistical mechanical distribution functions of a molecular system in contact with a plane, solid wall, is derived. The derivation involves an examination of the effect on the distribution functions produced by an infinitesimal change in the applied external potential. The resulting equations are similar in form to the well‐known Bogoliubov‐Born‐Green‐Kirkwood‐Yvon equations, specialized to the fluid‐wall problem. However, unlike the BBGKY equations, the equations presented here are not restricted by the pair potential condition. The application of these equations to fluid adsorption and to other aspects of liquid state physics is discussed in detail.