title: Investigation of electron density changes at the onset of a chemical reaction using the state-specific dual descriptor from conceptual density functional theory.
abstract: The electron density changes from reactants towards the transition state of a chemical reaction is expressed as a linear combination of the state-specific dual descriptors (SSDD) of the corresponding reactant complexes. Consequently, the SSDD can be expected to bear important resemblance to the so-called natural orbitals for chemical valence (NOCV), introduced as the orbitals that diagonalize the deformation density matrix of interacting molecules. This agreement is shown for three case studies: the complexation of a Lewis acid with a Lewis base, a SN2 nucleophilic substitution reaction and a Diels-Alder cycloaddition reaction. As such, the SSDD computed for reactant complexes are shown to provide important information about charge transfer interactions during a chemical reaction.
authors.affiliation: Research group of General Chemistry, Vrije Universiteit Brussel (VUB), Pleinlaan 2, B-1050 Brussels, Belgium. fdeprof@vub.ac.be.
authors.forename: Frank
authors.initials: F
authors.lastname: De Proft
authors.forename: Valérian
authors.initials: V
authors.lastname: Forquet
authors.forename: Benjamin
authors.initials: B
authors.lastname: Ourri
authors.forename: Henry
authors.initials: H
authors.lastname: Chermette
authors.forename: Paul
authors.initials: P
authors.lastname: Geerlings
authors.forename: Christophe
authors.initials: C
authors.lastname: Morell
mesh_terms: D004583:Electrons; D058116:Lewis Acids / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory
chemical_list: D058116:Lewis Acids