Ultrafast photoisomerization mechanism of azaborine revealed by nonadiabatic molecular dynamics simulations

1,2-Dihydro-1,2-azaborine is an isoelectronic analog of benzene with a B-N substitution, and its unique photoisomerization behavior, which is distinct from that of benzene, has drawn significant attention. To understand the detailed mechanism of azaborine photochemistry considering the dynamical eff...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2023-07, Vol.25 (26), p.1723-17237
Main Authors: Jeong, Sangmin, Park, Eunji, Kim, Joonghan, Kim, Kyung Hwan
Format: Article
Language:English
Subjects:
Algorithms
Benzene
Dynamic structural analysis
Hydrocarbons
Isomers
Mathematical analysis
Molecular dynamics
Photochemical reactions
Photochemistry
Simulation
Trajectory analysis
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Summary:1,2-Dihydro-1,2-azaborine is an isoelectronic analog of benzene with a B-N substitution, and its unique photoisomerization behavior, which is distinct from that of benzene, has drawn significant attention. To understand the detailed mechanism of azaborine photochemistry considering the dynamical effect and gain a comprehensive understanding of photochemical reactions, we investigated the photoisomerization dynamics of azaborine using nonadiabatic molecular dynamics simulations with Tully's surface hopping algorithm. Herein, the structural and energetic analyses of the trajectories revealed three different paths: direct relaxation (path 1), relaxation via a prefulvene-like intermediate (path 2), and formation of the Dewar isomer as a photoproduct (path 3). Our results confirmed that the photoisomerization of azaborine follows the energetically favored pathway predicted by the previous minimum energy path (MEP) calculations, exclusively forming the Dewar isomer, which is consistent with the experimental observations. Additionally, despite the low quantum yield found in our simulations, the high-level excitation energy calculations support the complete conversion observed in the experiments. Our non-adiabatic molecular dynamics simulations exploring the photoisomerization mechanism of azaborine demonstrates its distinct photochemical properties, as observed in experimental research, including the exclusive formation of the Dewar isomer.
ISSN:1463-9076
1463-9084
DOI:10.1039/d3cp01169k