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Analogies between photochemical reactions and ground-state post-transition-state bifurcations shed light on dynamical origins of selectivity

Nature Chemistry volume 16, pages 615–623 (2024)Cite this article

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Abstract

Revealing the origins of kinetic selectivity is one of the premier tasks of applied theoretical organic chemistry, and for many reactions, doing so involves comparing competing transition states. For some reactions, however, a single transition state leads directly to multiple products, in which case non-statistical dynamic effects influence selectivity control. The selectivity of photochemical reactions—where crossing between excited-state and ground-state surfaces occurs near ground-state transition structures that interconvert competing products—also should be controlled by the momentum of the reacting molecules as they return to the ground state in addition to the shape of the potential energy surfaces involved. Now, using machine-learning-assisted non-adiabatic molecular dynamics and multiconfiguration pair-density functional theory, these factors are examined for a classic photochemical reaction—the deazetization of 2,3-diazabicyclo[2.2.2]oct-2-ene—for which we demonstrate that momentum dominates the selectivity for hexadiene versus [2.2.2] bicyclohexane products.

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Fig. 1: Analogies between ground-state and excited-state reactions.
Fig. 2: Photochemical reactivity of DBO.
Fig. 3: Momentum effects.
Fig. 4: The complicated network of reactions accessible from 1,4-cyclohexanediyl.
Fig. 5: How good was our analogy?

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Data availability

Additional computational data are provided as online Supplementary Information, including information on neural network model validation, comparison of theoretical methods, data on potential energy surfaces, data on surface hopping points and coordinates for computed structures.

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Acknowledgements

We gratefully acknowledge support from the National Science Foundation (CHE-1856416 and supercomputing resources from the Extreme Science and Engineering Discovery Environment (XSEDE) and Advanced Cyberinfrastructure Coordination Ecosystem: Services & Support (ACCESS) programmes to D.J.T.). The preliminary work of D.J.T. and Z.F. on photochemical modelling was supported by the American Chemical Society’s Petroleum Research Fund (ACS-PRF, PRF no. 60663-ND4). We also thank S. Lopez and J. Li for their helpful suggestions.

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  1. Department of Chemistry, University of California, Davis, Davis, CA, USA

    Zhitao Feng, Wentao Guo, Wang-Yeuk Kong, Shunyang Wang & Dean J. Tantillo

  2. Department of Electrical and Computer Engineering, University of California, Davis, Davis, CA, USA

    Dongjie Chen

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Contributions

D.J.T. conceptualized the project. Z.F. designed the computational experiments with input from all authors. Z.F., W.G. and W.-Y.K. performed the calculations. All authors analysed and interpreted data. Z.F. draughted the original version of the paper. Z.F. and D.J.T. edited the paper with input from all authors.

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Feng, Z., Guo, W., Kong, WY. et al. Analogies between photochemical reactions and ground-state post-transition-state bifurcations shed light on dynamical origins of selectivity. Nat. Chem. 16, 615–623 (2024). https://doi.org/10.1038/s41557-023-01410-y

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