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Automatic generation of active coordinates for quantum dynamics calculations: application to the dynamics of benzene photochemistry

A new practical method to generate a subspace of active coordinates for quantum dynamics calculations is presented. These reduced coordinates are obtained as the normal modes of an analytical quadratic representation of the energy difference between excited and ground states within the complete active space self-consistent field method. At the Franck-Condon point, the largest negative eigenvalues of this Hessian correspond to the photoactive modes: those that reduce the energy difference and lead to the conical intersection; eigenvalues close to 0 correspond to bath modes, while modes with large positive eigenvalues are photoinactive vibrations, which increase the energy difference. The efficacy of quantum dynamics run in the subspace of the photoactive modes is illustrated with the photochemistry of benzene, where theoretical simulations are designed to assist optimal control experiments

© Journal of Chemical Physics, 2008, vol. 128, núm. 112

American Institute of Physics

Author: Lasorne, Benjamin
Sicilia, Fabrizio
Bearpark, Michael J.
Robb, Michael A.
Worth, Graham A.
Blancafort San José, Lluís
Date: 2008
Abstract: A new practical method to generate a subspace of active coordinates for quantum dynamics calculations is presented. These reduced coordinates are obtained as the normal modes of an analytical quadratic representation of the energy difference between excited and ground states within the complete active space self-consistent field method. At the Franck-Condon point, the largest negative eigenvalues of this Hessian correspond to the photoactive modes: those that reduce the energy difference and lead to the conical intersection; eigenvalues close to 0 correspond to bath modes, while modes with large positive eigenvalues are photoinactive vibrations, which increase the energy difference. The efficacy of quantum dynamics run in the subspace of the photoactive modes is illustrated with the photochemistry of benzene, where theoretical simulations are designed to assist optimal control experiments
Format: application/pdf
Citation: Lasorne, B., Sicilia, F., Bearpark, M.J., Robb, M.A., Worth, G.A., i Blancafort, L. (2008). Automatic generation of active coordinates for quantum dynamics calculations: application to the dynamics of benzene photochemistry. Journal of Chemical Physics, 128 (12), 124307. Recuperat 22 març 2011, a http://link.aip.org/link/doi/10.1063/1.2839607
ISSN: 0021-9606 (versió paper)
1089-7690 (versió electrònica)
Document access: http://hdl.handle.net/10256/3278
Language: eng
Publisher: American Institute of Physics
Collection: Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.2839607
Articles publicats (D-Q)
Is part of: © Journal of Chemical Physics, 2008, vol. 128, núm. 112
Rights: Tots els drets reservats
Subject: Benzè
Camp autoconsistent, Teoria del
Fotoquímica
Quàntums, Teoria dels
Benzene
Photochemistry
Quantum theory
Self-consistent field theory
Title: Automatic generation of active coordinates for quantum dynamics calculations: application to the dynamics of benzene photochemistry
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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