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Published in

American Institute of Physics, The Journal of Chemical Physics, 11(136), p. 114102

DOI: 10.1063/1.3694103

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

Journal article published in 2012 by Maria Hellgren ORCID, E. K. U. Gross
This paper is available in a repository.
This paper is available in a repository.

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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.