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Wave Packet Dynamics at an Extended Seam of Conical Intersection: Mechanism of the Light-Induced Wolff Rearrangement

Quantum dynamics calculations on a model surface based on CASPT(2)//CASSCF calculations are carried out to probe the traversal of a wave packet through an extended seam of conical intersection during the light-induced Wolff rearrangement of diazonaphtoquinone. The reaction is applied in the fabrication of integrated circuits. It consists of nitrogen elimination and ring rearrangement to yield a ketene. After excitation, the wave packet relaxes and reaches the extended seam. A fraction of the wave packet decays to the ground state at a region of the seam connected to a carbene intermediate, while the remaining part decays at a region leading to the ketene. The passage of the wave packet through the extended seam explains the competition between concerted ketene formation and a stepwise mechanism involving a carbene. The two primary photoproducts are formed in the first 100 fs of the simulation, in agreement with recent ultrafast spectroscopy measurements

This work has been supported by Grants CTQ2008-06696 and CTQ2011-26573 from the Spanish Ministerio de Ciencia e Innovacion (MICINN), SGR0528 from the Catalan Agencia de Gestio d’Ajuts Universitaris i de Recerca (AGAUR), and UNGI08-4E-003 from MICINN and the FEDER fund (European Fund for Regional Development). Q.L. acknowledges a Juan de la Cierva fellowship of the MICINN and A.M. a Beatriu de Pinos fellowship of the Generalitat de Catalunya (Spain)

© Journal of Physical Chemistry Letters, 2012, vol. 3, núm. 8, p. 1056-1061

American Chemical Society (ACS)

Author: Li, Quansong
Migani, Annapaola
Blancafort San José, Lluís
Date: 2012
Abstract: Quantum dynamics calculations on a model surface based on CASPT(2)//CASSCF calculations are carried out to probe the traversal of a wave packet through an extended seam of conical intersection during the light-induced Wolff rearrangement of diazonaphtoquinone. The reaction is applied in the fabrication of integrated circuits. It consists of nitrogen elimination and ring rearrangement to yield a ketene. After excitation, the wave packet relaxes and reaches the extended seam. A fraction of the wave packet decays to the ground state at a region of the seam connected to a carbene intermediate, while the remaining part decays at a region leading to the ketene. The passage of the wave packet through the extended seam explains the competition between concerted ketene formation and a stepwise mechanism involving a carbene. The two primary photoproducts are formed in the first 100 fs of the simulation, in agreement with recent ultrafast spectroscopy measurements
This work has been supported by Grants CTQ2008-06696 and CTQ2011-26573 from the Spanish Ministerio de Ciencia e Innovacion (MICINN), SGR0528 from the Catalan Agencia de Gestio d’Ajuts Universitaris i de Recerca (AGAUR), and UNGI08-4E-003 from MICINN and the FEDER fund (European Fund for Regional Development). Q.L. acknowledges a Juan de la Cierva fellowship of the MICINN and A.M. a Beatriu de Pinos fellowship of the Generalitat de Catalunya (Spain)
Format: application/pdf
ISSN: 1948-7185
Document access: http://hdl.handle.net/10256/11481
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MEC/PN 2009-2011/CTQ2008-06696
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/10.1021/jz300235z
Articles publicats (D-Q)
Is part of: © Journal of Physical Chemistry Letters, 2012, vol. 3, núm. 8, p. 1056-1061
Rights: Tots els drets reservats
Subject: Dinàmica molecular
Molecular dynamics
Espectroscòpia infraroja
Infrared spectroscopy
Rotació molecular
Molecular rotation
Title: Wave Packet Dynamics at an Extended Seam of Conical Intersection: Mechanism of the Light-Induced Wolff Rearrangement
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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