Abstract
Abstract We present a class of models for the surface of a liquid metal, which may be part of an electrochemical interface. The particles of the system, for the purpose of derivation of thermodynamic properties, are the charged ion cores, while the energy of the electrons is evaluated using the electron density functional formalism, previously principally applied to solids. An expression for the surface energy Us , defined as the energy required to create unit area of surface by separation of a volume of homogeneous metal into two parts, is derived (Eqs. 18–20). The surface tension γ is obtained by differentiating the Helmholtz free energy with respect to the area of the system, keeping volume and particle number constant (Eqs. 27–37). The surface tension is also equal to the difference between the free energy of the system containing a surface and the free energy of a reference system. It thus defines a surface energy through the Gibbs-Helmholtz equation, and this surface energy is shown to be identical ...
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