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


Autoria(s): Lasorne, Benjamin; Sicilia, Fabrizio; Bearpark, Michael J.; Robb, Michael A.; Worth, Graham A.; Blancafort San José, Lluís
Data(s)

2008

Resumo

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

Formato

application/pdf

Identificador

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

0021-9606 (versió paper)

1089-7690 (versió electrònica)

http://hdl.handle.net/10256/3278

http://dx.doi.org/10.1063/1.2839607

Idioma(s)

eng

Publicador

American Institute of Physics

Relação

Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.2839607

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

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Palavras-Chave #Benzè #Camp autoconsistent, Teoria del #Fotoquímica #Quàntums, Teoria dels #Benzene #Photochemistry #Quantum theory #Self-consistent field theory
Tipo

info:eu-repo/semantics/article