UC Berkeley

Unrestricted density functional theory (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 H₂ molecule. This is not a 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 H₂. The polarizability and force constant prediction failures appear to stem from incomplete spin localization into individual H atoms beyond the Coulson-Fischer 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 toward H atom association, indirectly also leading to incorrect forces. These unphysicalities suggest that the use of problematic functionals is probably unwise in ab initio dynamics calculations, especially if strong electrostatic interactions are possible.