Boundary condition effects in simulations of water confined between planar walls

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Abstract
In computer simulations of water between hydrophobic walls the results exhibit a strong dependence upon the boundary conditions applied. With the minimum image (MI) convention the water molecules tend to be orientationally ordered throughout the simulation cell (Valleau, J. P., and Gardner, A. A., 1987, J. chem. Phys., 86, 4162) whereas, if a spherical cut-off (SC) is applied, strong orientational order is found only in the immediate vicinity of the surface (Lee, C. Y., McCammon, J. A., and Rossky, P. J., 1984, J. chem. Phys., 80, 4448). These conflicting observations have remained unresolved, and clearly raise troubling questions concerning the validity of simulation results for water between surfaces of all types. In the present paper we explore this problem by carrying out a detailed analysis of the results obtained with various types of boundary condition. These include Ewald calculations carried out with a central simulation cell adapted to describe the slab geometry of interest. It is shown that the order observed in MI calculations is an artefact of that particular truncation. The reason for this is isolated and discussed. Similar problems are found if a cylindrical cut-off is employed. The Ewald and SC methods gave qualitatively similar results for systems similar to those considered in previous simulations. However, for some geometries problems can also arise with the SC method. We conclude that in general the slab-adapted Ewald method is the safest choice.

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