Effect of discontinuities in Kohn-Sham-based chemical reactivity theory

Abstract

We provide a new derivation of a formula for the Fukui function of density-functional chemical reactivity theory which incorporates the discontinuities in the Kohn-Sham reference system. Orbital relaxations are described in terms of the exchange-correlation (XC) kernel, i.e., the derivative of the XC potential with respect to the density and it is shown that in order to correctly measure the reactivity toward a nucleophilic reagent a discontinuity of the XC kernel has to be taken into account. The importance of this finding is illustrated in model molecular systems.