Atomic orbital self-energy and electronegativity

TL;DR

This paper uses density functional theory to accurately calculate atomic ionization energies, electron affinities, and electronegativities across the periodic table, comparing different computational methods and experimental data.

Contribution

It introduces a consistent approach to determine electronegativities directly from orbital self-energies using density functional theory, validated against various methods and data.

Findings

Electronegativities can be accurately obtained from orbital self-energies.

The methods show good agreement with experimental and other theoretical results.

Electronegativity trends are reliably predicted from hydrogen to xenon.

Abstract

In this work, atomic calculations were performed within the local-density and generalized-gradient approximations of exchange and correlation density functionals within density-functional theory to provide accurate periodic trends of first ionization energies and electron affinities of the atomic series from hydrogen to xenon. Electronegativities were determined directly from Mulliken's formula and were shown to be equivalently calculated rather by using Slater-Janak's transition state or by calculating the electrostatic self-energies of the orbitals involved in the transition to ions. Finally, comparisons were made with other theoretical and experimental results, including Mulliken-Jaff\'e's electronegativity scale.