Analytical Correlation in the H$_{2}$ Molecule from the Independent Atom Ansatz
Abstract
The independent atom ansatz of density functional theory yields an accurate analytical expression for dynamic correlation energy in the H molecule: for the atom-additive self-consistent density . Combined with exact atomic self-exchange, it recovers more than 99.5 % of nearly exact SCAN exchange-correlation energy at R > 0.5 , differing by less than 0.12 eV. The total energy functional correctly dissociates the H-H bond and yields absolute errors of 0.002 , 0.19 eV, and 13 cm relative to experiment at the tight binding computational cost. The chemical bond formation is attributed to the asymptotic Heitler-London resonance of quasi-orthogonal atomic states () with no contributions from kinetic energy or charge accumulation in the bond.
Cite
@article{arxiv.2405.15809,
title = {Analytical Correlation in the H$_{2}$ Molecule from the Independent Atom Ansatz},
author = {Alanna 'Lanie' Leung and Alexander V. Mironenko},
journal= {arXiv preprint arXiv:2405.15809},
year = {2024}
}
Comments
7 pages, 4 figures