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The response of the electronic structure to electronic excitation and double bond torsion in fulvene: A combined QTAIM, stress tensor and MO perspective

New insights into the double bond isomerization of fulvene in the ground and excited electronic states are provided by newly developed QTAIM and stress tensor tools. The S0 and S1 states follow the ’biradical’ torsion model, but the double bond is stiffer in the S0 state; by contrast, the S2 state follows the ’zwitterionic’ torsion. Differences are explained in terms of the ellipticity and bond critical point (BCP) stiffness for both QTAIM and the stress tensor. Overall, the wave-function based analysis is found to be in agreement with the work of Bonačić-Koutecký and Michl that the bond-twisted species can have biradical or zwitterionic character, depending on the state. Using QTAIM and the stress tensor a new understanding of bond torsion is revealed; the electronic charge density around the twisted bond is found not to rotate in concert with the nuclei of the rotated -CH2 methylene group. The ability to visualize how the bond stiffness varies between individual electronic states and how this correlates with the QTAIM and stress tensor bond stiffness is highlighted. In addition, the most and least preferred morphologies of bond-path torsion are visualized. Briefly we discuss the prospects for using this new QTAIM and stress tensor analysis for excited state chemistry

The One Hundred Talents Foundation of Hunan Province and the aid program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province are gratefully acknowledged for the support of S.J. and S. R. K. The National Natural Science Foundation of China is also gratefully acknowledged for the support of S.J. and S. R. K, project approval number: 21273069. L. B. acknowledges support from the Spanish Ministerio de Economia y Sostenibilidad (MINECO) (CTQ2011-26573 and UNGI08-4E-003 from FEDER (European Fund for Regional Development)), and the Catalan Agencia de Gestio d’Ajuts Universitaris i de Recerca (SGR0528) and Direccio General de la Recerca (Xarxa de Referencia en Quimica Teorica i Computacional de Catalunya)

© Physical Chemistry Chemical Physics, 2014, vol. 16, núm. 15, p. 7115-7126

Royal Society of Chemistry (RSC)

Autor: Jenkins, Samantha
Blancafort San José, Lluís
Kirk, Steven R
Bearpark, Michael J.
Data: 2014
Resum: New insights into the double bond isomerization of fulvene in the ground and excited electronic states are provided by newly developed QTAIM and stress tensor tools. The S0 and S1 states follow the ’biradical’ torsion model, but the double bond is stiffer in the S0 state; by contrast, the S2 state follows the ’zwitterionic’ torsion. Differences are explained in terms of the ellipticity and bond critical point (BCP) stiffness for both QTAIM and the stress tensor. Overall, the wave-function based analysis is found to be in agreement with the work of Bonačić-Koutecký and Michl that the bond-twisted species can have biradical or zwitterionic character, depending on the state. Using QTAIM and the stress tensor a new understanding of bond torsion is revealed; the electronic charge density around the twisted bond is found not to rotate in concert with the nuclei of the rotated -CH2 methylene group. The ability to visualize how the bond stiffness varies between individual electronic states and how this correlates with the QTAIM and stress tensor bond stiffness is highlighted. In addition, the most and least preferred morphologies of bond-path torsion are visualized. Briefly we discuss the prospects for using this new QTAIM and stress tensor analysis for excited state chemistry
The One Hundred Talents Foundation of Hunan Province and the aid program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province are gratefully acknowledged for the support of S.J. and S. R. K. The National Natural Science Foundation of China is also gratefully acknowledged for the support of S.J. and S. R. K, project approval number: 21273069. L. B. acknowledges support from the Spanish Ministerio de Economia y Sostenibilidad (MINECO) (CTQ2011-26573 and UNGI08-4E-003 from FEDER (European Fund for Regional Development)), and the Catalan Agencia de Gestio d’Ajuts Universitaris i de Recerca (SGR0528) and Direccio General de la Recerca (Xarxa de Referencia en Quimica Teorica i Computacional de Catalunya)
Format: application/pdf
ISSN: 1463-9076 (versió paper)
1463-9084 (versió electrònica)
Accés al document: http://hdl.handle.net/10256/11472
Llenguatge: eng
Editor: Royal Society of Chemistry (RSC)
Col·lecció: MICINN/PN 2012-2014/CTQ2011-26573
MEC/2008/UNGI08-4E-003
AGAUR/2009-2014/2009 SGR-528
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c4cp00003j
Articles publicats (D-Q)
És part de: © Physical Chemistry Chemical Physics, 2014, vol. 16, núm. 15, p. 7115-7126
Drets: Tots els drets reservats
Matèria: Química de l’estat excitat
Excited state chemistry
Fotoquímica
Photochemistry
Estructura electrònica
Electronic structure
Hidrocarburs
Hydrocarbons
Títol: The response of the electronic structure to electronic excitation and double bond torsion in fulvene: A combined QTAIM, stress tensor and MO perspective
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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