Exchange-correlation effects in interatomic energies for pure density functionals and their application to the molecular energy prediction

Abstract

In this proof-of-concept paper, we show how exchange-correlation effects can be simply recovered for interatomic energies within the interacting quantum atoms decomposition when local, gradient generalized, or meta-gradient generalized approximations are used in density functional theory (DFT) calculations. We also demonstrate how inhomogeneity and non-local effects can be introduced even from a pure local scheme, without resorting to any orbital information. Finally, we provide numerical evidence on a database of selected energetic molecules that this decomposition scheme can be efficiently used to build accurate models for the prediction of molecular energies from an initial "cheap" DFT calculation.

Keywords: exchange‐correlation effects; interacting quantum atoms (IQA); linear and non‐linear models; quantum theory of atoms‐in‐molecules (QTAIM); source function.