Well-behaved versus ill-behaved density functionals for single bond dissociation: Separating success from disaster functional by functional for stretched H$_2$

TL;DR

This paper investigates how different density functionals perform in modeling the dissociation of H₂, revealing that some widely used functionals produce unphysical results due to incomplete spin localization and density errors.

Contribution

The study identifies specific density functionals that fail to accurately describe H₂ dissociation, highlighting the importance of functional choice for reliable extit{ab initio} dynamics.

Findings

Some functionals predict artificial barriers in H₂ dissociation.

Certain functionals produce incorrect polarizabilities and force constants.

Failures are linked to incomplete spin localization and density inaccuracies.

Abstract

Unrestricted DFT methods are typically expected to describe the homolytic dissociation of nonpolar single bonds in neutral species with qualitative accuracy, due to the lack of significant delocalization error. We however find that many widely used density functional approximations fail to describe features along the dissociation curve of the simple H$_2$ molecule. This is not an universal failure of DFT in the sense that many classic functionals like PBE and B3LYP give very reasonable results, as do some more modern methods like MS2. However, some other widely used functionals like B97-D (empirically fitted) and TPSS (non-empirically constrained) predict qualitatively wrong static polarizabilities, force constants and some even introduce an artificial barrier against association of independent H atoms to form H$_2$. The polarizability and force constant prediction failures appear to stem from incomplete spin localization into individual H atoms beyond the Coulson-Fisher point, resulting in `fractionally bonded' species where the ionic contributions to the Slater determinant are not completely eliminated, unlike the case of unrestricted Hartree-Fock. These errors therefore appear to be a consequence of poor self-consistent density prediction by the problematic functional. The same reasons could potentially lead to spurious barriers towards H atom association, indirectly also leading to incorrect forces. These unphysicalities suggest that the use of problematic functionals is probably unwise in \textit{ab initio} dynamics calculations, especially if strong electrostatic interactions are possible.