Keywords

Density functional theory, Ideal gas, Equations of state, Thermodynamic functions, Fourier analysis, Intermolecular potentials, Crystal lattices, Two-phase systems, Chemical potential, Lennard-Jones fluid

Abstract

The recently developed chemical potential perturbation (CPP) method [S. G. Moore and D. R. Wheeler, J. Chem. Phys. 134, 114514 (2011) https://doi.org/10.1063/1.3561865] is extended to the lattice (Ewald) sum treatment of intermolecular potentials. The CPP method predicts chemical potentials for a range of composition points using the local (position-dependent) pressure tensor of an inhomogeneous system. When computing the local pressure tensor, one can use the Irving-Kirkwood (IK) or Harasima (H) contours of distributing the pressure. We compare these two contours and show that for a planar interface, the homogeneous pressure and resulting chemical potential can be approximated with the CPP method using either the IK or the H contour, though with the lattice sum method the H contour has much greater computational efficiency. The proposed methods are validated by calculating the chemical potentials of the Lennard-Jones fluid and extended simple point-charge (SPC/E) water, and results show a high level of agreement with respective equations of state.

Original Publication Citation

Stan G. Moore, Dean R. Wheeler; Chemical potential perturbation: Extension of the method to lattice sum treatment of intermolecular potentials. J. Chem. Phys. 28 April 2012; 136 (16): 164503. https://doi.org/10.1063/1.4704609

Document Type

Peer-Reviewed Article

Publication Date

2012-04-23

Publisher

American Institute of Physics

Language

English

College

Ira A. Fulton College of Engineering

Department

Chemical Engineering

University Standing at Time of Publication

Full Professor

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