title: 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.
authors.affiliation: Max Planck Institute of Microstructure Physics, Weinberg 2, 06120 Halle, Germany.
authors.forename: Maria
authors.initials: M
authors.lastname: Hellgren
authors.forename: E K U
authors.initials: EK
authors.lastname: Gross