Deriving bonding concepts for molecules, surfaces, and solids with energy decomposition analysis for extended systems

Abstract

Chemical bonding concepts like covalency, ionicity, Pauli repulsion, shared‐electron, or donor–acceptor bonding are important tools to sort our vast knowledge in chemistry and predict new reactivity. Electronic structure analysis provides the basis for a detailed understanding of the origins of these concepts. Energy decomposition analysis (EDA) is an established method for molecules and has recently been implemented for application in extended systems, that is, surfaces and solids, where it is termed periodic EDA (pEDA). The foundations and applications of this method which enables the derivation of bonding concepts are outlined in this review. Embedded in key examples from molecular and solid‐state chemistry, the major part covers the adsorption and reactivity of molecules with surfaces with a focus on organic molecules interacting with semiconductor surfaces. Based on electronic structure analysis and supported by a quantitative methodology, we show that analogous bonding concepts can be applied in diverse chemical environments. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Structure and Mechanism > Computational Materials Science