Jump to main content
Jump to site search

Issue 32, 2011
Previous Article Next Article

A non-adiabatic quantum-classical dynamics study of the intramolecular excited state hydrogen transfer in ortho-nitrobenzaldehyde

Author affiliations

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 S1 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 S1 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.

Graphical abstract: A non-adiabatic quantum-classical dynamics study of the intramolecular excited state hydrogen transfer in ortho-nitrobenzaldehyde

Back to tab navigation

Supplementary files

Publication details

The article was received on 04 Mar 2011, accepted on 13 Jun 2011 and first published on 06 Jul 2011


Article type: Paper
DOI: 10.1039/C1CP20620F
Citation: Phys. Chem. Chem. Phys., 2011,13, 14685-14693
  •   Request permissions

    A non-adiabatic quantum-classical dynamics study of the intramolecular excited state hydrogen transfer in ortho-nitrobenzaldehyde

    V. Leyva, I. Corral, F. Feixas, A. Migani, L. Blancafort, J. González-Vázquez and L. González, Phys. Chem. Chem. Phys., 2011, 13, 14685
    DOI: 10.1039/C1CP20620F

Search articles by author

Spotlight

Advertisements