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Electron delocalization and aromaticity in low-lying excited states of archetypal organic compounds

Aromaticity is a property usually linked to the ground state of stable molecules. Although it is well-known that certain excited states are unquestionably aromatic, the aromaticity of excited states remains rather unexplored. To move one step forward in the comprehension of aromaticity in excited states, in this work we analyze the electron delocalization and aromaticity of a series of low-lying excited states of cyclobutadiene, benzene, and cyclooctatetraene with different multiplicities at the CASSCF level by means of electron delocalization measures. While our results are in agreement with Baird’s rule for the aromaticity of the lowest-lying triplet excited state in annulenes having 4nπ-electrons, they do not support Soncini and Fowler’s generalization of Baird’s rule pointing out that the lowest-lying quintet state of benzene and septet state of cyclooctatetraene are not aromatic

The following organizations are thanked for financial support: the Ministerio de Ciencia e Innovacion (MICINN, projects number CTQ2008-03077/BQU and CTQ2011-23156/BQU), and the DIUE of the Generalitat de Catalunya (project number 2009SGR637). Excellent service by the Centre de Serveis Cientifics i Academics de Catalunya (CESCA) is gratefully acknowledged. Support for the research of M. Sola was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya

© Physical Chemistry Chemical Physics, 2011, vol. 13, núm. 46, p. 20690-20703

Royal Society of Chemistry (RSC)

Manager: Ministerio de Educación y Ciencia (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Author: Feixas Geronès, Ferran
Vandenbussche, Jelle
Bultinck, Patrick
Matito i Gras, Eduard
Solà i Puig, Miquel
Date: 2011
Abstract: Aromaticity is a property usually linked to the ground state of stable molecules. Although it is well-known that certain excited states are unquestionably aromatic, the aromaticity of excited states remains rather unexplored. To move one step forward in the comprehension of aromaticity in excited states, in this work we analyze the electron delocalization and aromaticity of a series of low-lying excited states of cyclobutadiene, benzene, and cyclooctatetraene with different multiplicities at the CASSCF level by means of electron delocalization measures. While our results are in agreement with Baird’s rule for the aromaticity of the lowest-lying triplet excited state in annulenes having 4nπ-electrons, they do not support Soncini and Fowler’s generalization of Baird’s rule pointing out that the lowest-lying quintet state of benzene and septet state of cyclooctatetraene are not aromatic
The following organizations are thanked for financial support: the Ministerio de Ciencia e Innovacion (MICINN, projects number CTQ2008-03077/BQU and CTQ2011-23156/BQU), and the DIUE of the Generalitat de Catalunya (project number 2009SGR637). Excellent service by the Centre de Serveis Cientifics i Academics de Catalunya (CESCA) is gratefully acknowledged. Support for the research of M. Sola was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya
Format: application/pdf
Citation: 015424
ISSN: 1463-9076 (versió paper)
1463-9084 (versió electrònica)
Document access: http://hdl.handle.net/10256/11403
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: MEC/PN 2009-2011/CTQ2008-03077/BQU
MICINN/PN 2012-2014/CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c1cp22239b
Articles publicats (D-Q)
Is part of: © Physical Chemistry Chemical Physics, 2011, vol. 13, núm. 46, p. 20690-20703
Rights: Tots els drets reservats
Subject: Aromaticitat (Química)
Aromaticity (Chemistry)
Compostos orgànics
Organic compounds
Title: Electron delocalization and aromaticity in low-lying excited states of archetypal organic compounds
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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