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DFT-based chemical reactivity indices in the Hartree-Fock method. II. Fukui function, chemical potential, and
Robert Balawender1, Paul Geerlings
1Institute of Physical Chemistry of the Polish Academy of Sciences (PAS), Kasprzaka 44/52, PL-01-224 Warsaw, Poland. balawend@ichf.edu.pl
Abstract:
A derivation of the density-functional-theory- (DFT) based reactivity indices in the ensemble unrestricted Hartree-Fock (eUHF) method is presented. The comparison between the properties of the reactivity indices evaluated in one and two sets of spin-orbital approach of the eUHF and hyper-unrestricted Hartree-Fock (UHF) methods are shown. All approaches give similar Fukui function irrespective of methodology used, but significantly differ for the global indices, containing important chemical information, and so their interpretation in terms of DFT- based indices can be questionable. The calculation scheme for the indices using the first- and second-order coupled perturbed eHF equations is proposed. A method for the identification of the spinorbitals involved in the change of the total number of electrons is included. The illustrative examples (water and hydrogen cyanide) show that the ground-state (GS) properties of the (Z +/- 1)-electron systems can be predicted from the GS properties of the Z-electron systems with an accuracy comparable with the UHF calculations. The relaxation effect, important for the HCN system in which a change in the symmetry of the highest-occupied spin-orbital occurs, is effectively predicted.
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