Journal of Chemical Physics, Vol.107, No.19, 7967-7974, 1997
Total and direct correlations in the liquid-vapor interface and the capillary-wave theory
The two-point total correlation function (H) over tilde(1,2) = [delta(rho-k)delta rho(k)] = H(z(1),z(2),k) in the interfacial zone between a Lennard-Jones liquid and its coexisting vapor is determined in a molecular dynamics simulation at a low temperature T = 0.75. New terms absent in the standard capillary wave theory are discovered. Eigenvector analysis and matrix partitioning of H and of the direct correlation function C revealed a strong k(2) dependence at k --> 0 in a set-of terms proportional to rho'rho', rho ''rho '', rho'''rho''',.... The bending coefficient is found nonexistent. Projections of H, C, and susceptibilities are discussed in the context of removal of all capillary wave contributions to obtain intrinsic quantities. (C) 1997 American Institute of Physics.