A periodic Energy Decomposition Analysis (pEDA) method for the Investigation of Chemical Bonding in Extended Systems

TL;DR

This paper introduces a new periodic energy decomposition analysis (pEDA) method based on density functional theory, capable of analyzing chemical bonding in extended systems with various bonding scenarios.

Contribution

The paper presents a novel pEDA scheme that handles periodic boundary conditions and fragment occupations, enabling detailed bonding analysis in extended systems.

Findings

pEDA provides results comparable to established methods for molecular systems.

The method shows good convergence with basis set, integration, and k-space sampling.

It effectively analyzes bonding in metallic, semiconducting, and insulating surfaces.

Abstract

The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the binding energy between two fragments (e.g. the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic and dispersion interaction, Pauli repulsion and orbital relaxation energies. The pEDA presented here for an AO-based implementation can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy and k-space sampling. Four typical bonding scenarios for surface adsorbate complexes were chosen to highlight the performance of the method representing insulating (CO on MgO(001)), metallic (H$_2$ on M(001), M = Pd, Cu) and semiconducting (CO and C$_2$H$_2$ on Si(001)c(4x2)) substrates. These examples cover the regimes of metallic, semiconducting and insulating substrates as well as bonding scenarios ranging from weakly interacting to covalent (shared electron and donor acceptor) bonding. The results presented lend confidence, that the pEDA will be a powerful tool for the analysis of surface-adsorbate binding in the future, enabling the transfer of concepts like ionic and covalent binding, donor-acceptor interaction, steric repulsion and others to extended systems.