title: Quantifying electro/nucleophilicity by partitioning the dual descriptor.
abstract: Translating local electro/nucleophilicities into the language of reactive sites is an appealing theoretical challenge that could be conducive to strengthen the collaborative dialogue between experimentalists and quantum chemists. The usual schemes for such condensation, relying on atomic charges, may however lead to important information loss, due to a sometimes inappropriate averaging of the reactivity anisotropy. In this article, we present instead an approach based on the dual descriptor Δf, which aims at partitioning real space into nonoverlapping reactive domains that feature a constant Δf sign. This strategy enables not only to identify the nucleo/electrophilic regions inside a molecule but also to quantify meaningful properties (mean value, volume, electron population…). Its interest is then illustrated on two specific chemical problems: the measure of σ-holes in the context of halogen bonds, and of the electrophilicity of organic carbocations, casting the light on the versatility of this method.
authors: Normandy University, COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesniére, 76821, Mont St Aignan, Cedex, France.
authors: Vincent
authors: V
authors: Tognetti
authors: Christophe
authors: C
authors: Morell
authors: Laurent
authors: L
authors: Joubert
keywords: atomic condensation; carbocations; conceptual DFT; dual descriptor; electrophilicity; grid algorithm; halogen bonds; nucleophilicity; σ-holes