title: Characterization of the Chemical Behavior of the Low Excited States through a Local Chemical Potential.
abstract: Exploiting the locality of the chemical potential of an excited state when it is evaluated using the ground-state density functional theory (DFT), a new descriptor for excited states has been proposed. This index is based on the assumption that the relaxation of the electronic density drives the chemical reactivity of excited states. The sign of the descriptor characterizes the electrophilic or nucleophilic behavior of the atomic regions. A relation between the new descriptor and the dual descriptor is derived and provides a posteriori justification of its use to rationalize the Woodward-Hoffmann rules for photochemical reactions within the conceptual DFT. Finally, the descriptor is successfully applied to some [2 + 2] photocycloadditions, like Paterno-Büchi reactions.
authors.affiliation: Commissariat à L'Énergie Atomique Grenoble, 17, Rue des Martyrs, F-38054 Grenoble Cedex 9, France, Department of Chemistry, McMaster University, Hamilton, Ontario, L8S 4M1, Eenheid Algemene Chemie, Vrije Universiteit Brussel, Faculteit Wetenschappen Pleinlaan 2, 1050 Brussels, Belgium, Member of the QCMM Alliance Ghent-Brussels Belgium, and Université de Lyon, Université Lyon 1, Sciences Analytiques CNRS UMR 5180 Chimie Physique Théorique, F-69622 Villeurbanne Cedex, France.
authors.forename: Christophe
authors.initials: C
authors.lastname: Morell
authors.affiliation: Commissariat à L'Énergie Atomique Grenoble, 17, Rue des Martyrs, F-38054 Grenoble Cedex 9, France, Department of Chemistry, McMaster University, Hamilton, Ontario, L8S 4M1, Eenheid Algemene Chemie, Vrije Universiteit Brussel, Faculteit Wetenschappen Pleinlaan 2, 1050 Brussels, Belgium, Member of the QCMM Alliance Ghent-Brussels Belgium, and Université de Lyon, Université Lyon 1, Sciences Analytiques CNRS UMR 5180 Chimie Physique Théorique, F-69622 Villeurbanne Cedex, France.
authors.forename: Vanessa
authors.initials: V
authors.lastname: Labet
authors.affiliation: Commissariat à L'Énergie Atomique Grenoble, 17, Rue des Martyrs, F-38054 Grenoble Cedex 9, France, Department of Chemistry, McMaster University, Hamilton, Ontario, L8S 4M1, Eenheid Algemene Chemie, Vrije Universiteit Brussel, Faculteit Wetenschappen Pleinlaan 2, 1050 Brussels, Belgium, Member of the QCMM Alliance Ghent-Brussels Belgium, and Université de Lyon, Université Lyon 1, Sciences Analytiques CNRS UMR 5180 Chimie Physique Théorique, F-69622 Villeurbanne Cedex, France.
authors.forename: André
authors.initials: A
authors.lastname: Grand
authors.affiliation: Commissariat à L'Énergie Atomique Grenoble, 17, Rue des Martyrs, F-38054 Grenoble Cedex 9, France, Department of Chemistry, McMaster University, Hamilton, Ontario, L8S 4M1, Eenheid Algemene Chemie, Vrije Universiteit Brussel, Faculteit Wetenschappen Pleinlaan 2, 1050 Brussels, Belgium, Member of the QCMM Alliance Ghent-Brussels Belgium, and Université de Lyon, Université Lyon 1, Sciences Analytiques CNRS UMR 5180 Chimie Physique Théorique, F-69622 Villeurbanne Cedex, France.
authors.forename: Paul W
authors.initials: PW
authors.lastname: Ayers
authors.affiliation: Commissariat à L'Énergie Atomique Grenoble, 17, Rue des Martyrs, F-38054 Grenoble Cedex 9, France, Department of Chemistry, McMaster University, Hamilton, Ontario, L8S 4M1, Eenheid Algemene Chemie, Vrije Universiteit Brussel, Faculteit Wetenschappen Pleinlaan 2, 1050 Brussels, Belgium, Member of the QCMM Alliance Ghent-Brussels Belgium, and Université de Lyon, Université Lyon 1, Sciences Analytiques CNRS UMR 5180 Chimie Physique Théorique, F-69622 Villeurbanne Cedex, France.
authors.forename: Frank
authors.initials: F
authors.lastname: De Proft
authors.affiliation: Commissariat à L'Énergie Atomique Grenoble, 17, Rue des Martyrs, F-38054 Grenoble Cedex 9, France, Department of Chemistry, McMaster University, Hamilton, Ontario, L8S 4M1, Eenheid Algemene Chemie, Vrije Universiteit Brussel, Faculteit Wetenschappen Pleinlaan 2, 1050 Brussels, Belgium, Member of the QCMM Alliance Ghent-Brussels Belgium, and Université de Lyon, Université Lyon 1, Sciences Analytiques CNRS UMR 5180 Chimie Physique Théorique, F-69622 Villeurbanne Cedex, France.
authors.forename: Paul
authors.initials: P
authors.lastname: Geerlings
authors.affiliation: Commissariat à L'Énergie Atomique Grenoble, 17, Rue des Martyrs, F-38054 Grenoble Cedex 9, France, Department of Chemistry, McMaster University, Hamilton, Ontario, L8S 4M1, Eenheid Algemene Chemie, Vrije Universiteit Brussel, Faculteit Wetenschappen Pleinlaan 2, 1050 Brussels, Belgium, Member of the QCMM Alliance Ghent-Brussels Belgium, and Université de Lyon, Université Lyon 1, Sciences Analytiques CNRS UMR 5180 Chimie Physique Théorique, F-69622 Villeurbanne Cedex, France.
authors.forename: Henry
authors.initials: H
authors.lastname: Chermette