Properties of Local Electronic Structures

TL;DR

This paper demonstrates that local electronic properties derived from molecular orbitals provide effective atomic fingerprints and better insights into chemical reactions than atomic orbital-based schemes, advancing molecular property analysis.

Contribution

It introduces a method to derive local electronic properties from molecular orbitals for atomic fingerprinting and reaction analysis, outperforming atomic orbital-based approaches.

Findings

Molecular orbital-based local properties yield unique atomic fingerprints.

Atomic orbital schemes often fail to distinguish atomic environments.

Molecular orbital schemes effectively decompose chemical reactions into atomic contributions.

Abstract

The simulation of intrinsic contributions to molecular properties holds the potential to allow for chemistry to be directly inferred from changes to electronic structures at the atomic level. In the present study, we demonstrate how such local properties can be readily derived from suitable molecular orbitals to yield effective fingerprints of various types of atoms in organic molecules. In contrast, corresponding inferences from schemes that instead make use of individual atomic orbitals for this purpose are generally found to fail in expressing much uniqueness in atomic environments. By further studying the extent to which entire chemical reactions may be decomposed into meaningful and continuously evolving atomic contributions, schemes based on molecular rather than atomic orbitals are once again found to be the more consistent, even allowing for intricate differences between seemingly uniform nucleophilic substitutions to be probed.