Role of Ultrafast Internal Conversion and Intersystem Crossing in the Nonadiabatic Relaxation Dynamics of ortho-Nitrobenzaldehyde

Author(s): Dóra Vörös, Sebastian Mai
Abstract: ortho-Nitrobenzaldehyde (oNBA) is a well-known photoactivated acid and a prototypical photolabile nitro-aromatic compound. Despite extensive investigations, the ultrafast relaxation dynamics of oNBA is still not properly understood, especially concerning the role of the triplet states. In this work, we provide an in-depth picture of this dynamics by combining single- and multireference electronic structure methods with potential energy surface exploration and nonadiabatic dynamics simulations using the Surface Hopping including ARbitary Couplings (SHARC) approach. Our results reveal that the initial decay from the bright ππ* state to the S₁ minimum is barrierless. It involves three changes in electronic structure from ππ* (ring) to nπ* (nitro group), to nπ* (aldehyde group), and then to another nπ* (nitro group). The decay of the ππ* takes 60-80 fs and can be tracked with time-resolved luminescence spectroscopy, where we predict for the first time a short-lived coherence of the luminescence energy with a 25 fs period. Intersystem crossing can occur already during the S₄ → S₁ deactivation cascade but also from S₁, with a time constant of about 2.4 ps and such that first a triplet ππ* state localized on the nitro group is populated. The triplet population first evolves into an nπ* and then quickly undergoes hydrogen transfer to form a biradical intermediate, from where the ketene is eventually produced. The majority of the excited population decays from S₁ through two conical intersections of equal utilization, a previously unreported one involving a scissoring motion of the nitro group that leads back to the oNBA ground state and the one involving hydrogen transfer that leads to the ketene intermediate.
Organisation(s): Computational and Soft Matter Physics, Department of Theoretical Chemistry
Journal: Journal of Physical Chemistry A
Volume: 127
Pages: 5872-5886
No. of pages: 15
ISSN: 1089-5639
DOI: https://doi.org/10.1021/acs.jpca.3c02899
Publication date: 07-2023
Peer reviewed: Yes
Austrian Fields of Science 2012: 104017 Physical chemistry
ASJC Scopus subject areas: Physical and Theoretical Chemistry
Portal url: https://ucrisportal.univie.ac.at/en/publications/9e5aee8b-24e8-4395-8c4e-4dabfb3a59f2