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 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.