Analytical Correlation in the H_{2} Molecule from the Independent Atom Ansatz
Abstract
A density functional theory approach using an analytical expression for dynamic correlation energy in H₂ achieves high accuracy with minimal computational cost and correctly dissociates the H-H bond.
The independent atom ansatz of density functional theory yields an accurate analytical expression for dynamic correlation energy in the H_{2} molecule: E_{c} = 0.5(1 - 2)(ab|ba) for the atom-additive self-consistent density 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, 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, 0.19 eV, and 13 cm^{-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 (- (ab|ba)) with no contributions from kinetic energy or charge accumulation in the bond.
Models citing this paper 0
No model linking this paper
Datasets citing this paper 0
No dataset linking this paper
Spaces citing this paper 0
No Space linking this paper
Collections including this paper 0
No Collection including this paper