Density-functional embedding using a plane-wave basis

TL;DR

This paper applies a plane-wave basis to the density-functional embedding method, demonstrating that non-local kinetic energy functionals can accurately reproduce Kohn-Sham results for bulk aluminium.

Contribution

It introduces a plane-wave implementation of the embedding method with local and non-local pseudopotentials, improving accuracy in reproducing Kohn-Sham energies and densities.

Findings

Non-local kinetic energy functionals yield total energies within 0.1 eV per atom.

Good agreement between embedded and Kohn-Sham electron densities.

Method effectively models substrate-embedded system interactions.

Abstract

The constrained electron density method of embedding a Kohn-Sham system in a substrate system (first described by P. Cortona, Phys. Rev. B {\bf 44}, 8454 (1991) and T.A. Wesolowski and A. Warshel, J. Phys. Chem {\bf 97}, 8050 (1993)) is applied with a plane-wave basis and both local and non-local pseudopotentials. This method divides the electron density of the system into substrate and embedded electron densities, the sum of which is the electron density of the system of interest. Coupling between the substrate and embedded systems is achieved via approximate kinetic energy functionals. Bulk aluminium is examined as a test case for which there is a strong interaction between the substrate and embedded systems. A number of approximations to the kinetic-energy functional, both semi-local and non-local, are investigated. It is found that Kohn-Sham results can be well reproduced using a non-local kinetic energy functional, with the total energy accurate to better than 0.1 eV per atom and good agreement between the electron densities.