title: A non-adiabatic quantum-classical dynamics study of the intramolecular excited state hydrogen transfer in ortho-nitrobenzaldehyde.
abstract: Ab initio surface-hopping dynamics calculations have been performed to simulate the intramolecular excited state hydrogen transfer dynamics of ortho-nitrobenzaldehyde (o-NBA) in the gas phase from the electronic S(1) excited state. Upon UV excitation, the hydrogen is transferred from the aldehyde substituent to the nitro group, generating o-nitrosobenzoic acid through a ketene intermediate. The semiclassical propagations show that the deactivation from the S(1) is ultrafast, in agreement with the experimental measurements, which detect the ketene in less than 400 fs. The trajectories show that the deactivation mechanism involves two different conical intersections. The first one, a planar configuration with the hydrogen partially transferred, is responsible for the branching between the formation of a biradical intermediate and the regeneration of the starting material. The conversion of the biradical to the ketene corresponds to the passage through a second intersection region in which the ketene group is formed.
authors: Institut für Physikalische Chemie, Friedrich Schiller Universität Jena, Helmholtzweg 4, 07743 Jena, Germany.
authors: Verónica
authors: V
authors: Leyva
authors: Inés
authors: I
authors: Corral
authors: Ferran
authors: F
authors: Feixas
authors: Annapaola
authors: A
authors: Migani
authors: Lluís
authors: L
authors: Blancafort
authors: Jesús
authors: J
authors: González-Vázquez
authors: Leticia
authors: L
authors: González
mesh_terms: D001547:Benzaldehydes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory
chemical_list: D001547:Benzaldehydes; C043850:2-nitrobenzaldehyde; D006859:Hydrogen