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arXiv · 2003.12305

Nonlocal density functional theory of water taking into account many-body dipole correlations: Binodal and surface tension of 'liquid-vapour' interface

Yu. A. Budkov·A. L. Kolesnikov
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Abstract

In this paper we formulate a nonlocal density functional theory of inhomogeneous water. We model a water molecule as a couple of oppositely charged sites. The negatively charged sites interact with each other through the Lennard-Jones potential (steric and dispersion interactions), square-well potential (short-range specific interactions due to electron charge transfer), and Coulomb potential, whereas the positively charged sites interact with all types of sites by applying the Coulomb potential only. Taking into account the nonlocal packing effects via the fundamental measure theory (FMT), dispersion and specific interactions in the mean-field approximation, and electrostatic interactions at the many-body level through the random phase approximation, we describe the liquid-vapour interface. We demonstrate that our model without explicit account of the association of water molecules due to hydrogen bonding and with explicit account of the many-body electrostatic interactions at the many-body level is able to describe the liquid-vapour coexistence curve and the surface tension at the ambient pressures and temperatures. We obtain very good agreement with available in the literature MD simulation results for density profile of liquid-vapour interface at ambient state parameters. The formulated theory can be used as a theoretical background for describing of the capillary phenomena, occurring in micro- and mesoporous materials.

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Yu. A. Budkov, A. L. Kolesnikov. 2020-03-27. Nonlocal density functional theory of water taking into account many-body dipole correlations: Binodal and surface tension of 'liquid-vapour' interface. https://doi.org/10.1088/1361-648x/ab884a

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