通过局部化学势对低激发态的化学行为进行表征。

Characterization of the Chemical Behavior of the Low Excited States through a Local Chemical Potential.

作者信息

Morell Christophe, Labet Vanessa, Grand André, Ayers Paul W, De Proft Frank, Geerlings Paul, Chermette Henry

机构信息

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.

出版信息

J Chem Theory Comput. 2009 Sep 8;5(9):2274-83. doi: 10.1021/ct900248a.

DOI:10.1021/ct900248a

PMID:26616614

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.

摘要

利用基态密度泛函理论（DFT）评估激发态化学势的局域性，提出了一种新的激发态描述符。该指标基于电子密度弛豫驱动激发态化学反应性的假设。描述符的符号表征了原子区域的亲电或亲核行为。推导了新描述符与对偶描述符之间的关系，并为其用于在概念DFT内合理化光化学反应的伍德沃德-霍夫曼规则提供了事后依据。最后，该描述符成功应用于一些[2 + 2]光环加成反应，如帕特诺-比希反应。