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Analytical Correlation in the H$_{2}$ Molecule from the Independent Atom Ansatz

Chemical Physics 2024-05-28 v1 Quantum Physics

Abstract

The independent atom ansatz of density functional theory yields an accurate analytical expression for dynamic correlation energy in the H2_{2} molecule: Ec=0.5(12)(abba)E_{c} = 0.5(1 - \sqrt{2})(ab|ba) for the atom-additive self-consistent density ρ=a2+b2\rho = |a|^{2} + |b|^{2}. Combined with exact atomic self-exchange, it recovers more than 99.5 % of nearly exact SCAN exchange-correlation energy at R > 0.5 A˚\r{A}, differing by less than 0.12 eV. The total energy functional correctly dissociates the H-H bond and yields absolute errors of 0.002 A˚\r{A}, 0.19 eV, and 13 cm1^{-1} 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 ((abba)- (ab|ba)) with no contributions from kinetic energy or charge accumulation in the bond.

Keywords

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