Practical failures from the inclusion of exact exchange: how much exact exchange is appropriate?

Abstract

The influence of exact exchange incorporated into exchange—correlation functionals on the predictions of relative energies, structures, electronic states, and vibrational spectra is examined numerically. Failures of widely used hybrid exchange—correlation functionals due to either the physical unacceptability of including exact exchange or an unbalanced mixing of exact exchange are considered. One set of examples involves tetraatomic chalcogen clusters and charge transfer complexes between diatomic chalcogens and diatomic oxygen. Poor energetic predictions from Hartree-Fock rule against the inclusion of exact exchange into the exchange—correlation functionals for these systems with significant left—right electron correlation effects. The energies of the conformers of [10]annulene are considered from an unusual viewpoint, namely, the empirical adjustment of the admixture of exact exchange to match the predictions of very high level theoretical methods. For this annulene with insignificant left-right electron correlation effects, a greater (50%) percentage of exact exchange should be included. The relationship of symmetry breaking to the inclusion of exact exchange is examined for seven linear radicals, OXO (X = B, Al, Ga, In, TI). AIOS, and OAIS. exchange—correlation functionals generate symmetry adapted solutions at the expense of an unusual ordering of the Kohn-Sham orbitals, which can cause uncharacteristic electronic states, incorrect vibrational spectra, and poorer predictions of energetics. These effects are greater when exact exchange is included. In all the examples considered, the appropriate focus for a detailed discussion of molecular properties involves consideration of the effects of exact exchange.