Crystal Orbital Hamilton Population (COHP) Analysis As Projected from Plane-Wave Basis Sets

Abstract

Simple, yet predictive bonding models are essential achievements of chemistry. In the solid state, in particular, they often appear in the form of visual bonding indicators. Because the latter require the crystal orbitals to be constructed from local basis sets, the application of the most popular density-functional theory codes (namely, those based on plane waves and pseudopotentials) appears as being ill-fitted to retrieve the chemical bonding information. In this paper, we describe a way to re-extract Hamilton-weighted populations from plane-wave electronic-structure calculations to develop a tool analogous to the familiar crystal orbital Hamilton population (COHP) method. We derive the new technique, dubbed "projected COHP" (pCOHP), and demonstrate its viability using examples of covalent, ionic, and metallic crystals (diamond, GaAs, CsCl, and Na). For the first time, this chemical bonding information is directly extracted from the results of plane-wave calculations.