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Observation of resonances in the transition state region of the F + NH3 reaction using anion photoelectron spectroscopy

Nature Chemistry volume 15, pages 194–199 (2023)Cite this article

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Abstract

The transition state of a chemical reaction is a dividing surface on the reaction potential energy surface (PES) between reactants and products and is thus of fundamental interest in understanding chemical reactivity. The transient nature of the transition state presents challenges to its experimental characterization. Transition-state spectroscopy experiments based on negative-ion photodetachment can provide a direct probe of this region of the PES, revealing the detailed vibrational structure associated with the transition state. Here we study the F + NH3 → HF + NH2 reaction using slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled FNH3− anions. Reduced-dimensionality quantum dynamical simulations performed on a global PES show excellent agreement with the experimental results, enabling the assignment of spectral structure. Our combined experimental–theoretical study reveals a manifold of vibrational Feshbach resonances in the product well of the F + NH3 PES. At higher energies, the spectra identify features attributed to resonances localized across the transition state and into the reactant complex that may impact the bimolecular reaction dynamics.

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Fig. 1: Energy diagram for photodetachment of FNH3− onto the transition-state region of the neutral F + NH3 reaction.
Fig. 2: Photodetachment spectra of FNH3−.
Fig. 3: 2D plots of F + NH3 wavefunctions accessed via photodetachment.

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Data availability

Data are provided with this paper and can be downloaded at https://doi.org/10.5281/zenodo.7332846. Source data are provided with this paper.

Code availability

The associated code, such as the subroutine to generate anion and neutral PESs and the quantum scattering code, is available on GitHub at https://github.com/apmtcc/AB-CDE and described in the README file.

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Acknowledgements

We thank the Air Force Office of Scientific Research for support via grants nos. FA9550-19-1-0051 (D.M.N.) and FA9550-22-1-0350 (H.G.). We also thank the National Natural Science Foundation of China for support under grants nos. 21973109 and 21921004 (H.S.). M.C.B. thanks the Army Research Office for a National Defense Science and Engineering Graduate fellowship. J.A.L. thanks the Alexander von Humboldt Foundation for a Feodor Lynen Research Fellowship.

Author information

Author notes

  1. Mark C. Babin

    Present address: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA

  2. Marissa L. Weichman

    Present address: Department of Chemistry, Princeton University, Princeton, NJ, USA

  3. Jongjin B. Kim

    Present address: KLA Corporation, Milpitas, CA, USA

Authors and Affiliations

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

    Mark C. Babin, Martin DeWitt, Jascha A. Lau, Marissa L. Weichman, Jongjin B. Kim & Daniel M. Neumark

  2. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan, China

    Hongwei Song

  3. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, USA

    Hua Guo

  4. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Daniel M. Neumark

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Contributions

M.C.B., M.D. and J.A.L. performed analysis of the data collected by M.L.W. and J.B.K., with support from D.M.N. All calculations were performed and analysed by H.S. with assistance from H.G. The paper was written by M.C.B. and H.S. with assistance from H.G. and D.M.N.

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Correspondence to Hongwei Song or Daniel M. Neumark.

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Nature Chemistry thanks Gabor Czako, Xueming Yang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Discussion, Figs. 1–4, Tables 1–3 and references.

Source data

Source Data Fig. 1

Theoretical data of neutral reactive potential energy surface.

Source Data Fig. 2

Experimental and theoretical photoelectron spectra of the title reaction.

Source Data Fig. 3

Computed anion and resonance wavefunctions as well as reactive potential energy surface.

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Babin, M.C., DeWitt, M., Lau, J.A. et al. Observation of resonances in the transition state region of the F + NH3 reaction using anion photoelectron spectroscopy. Nat. Chem. 15, 194–199 (2023). https://doi.org/10.1038/s41557-022-01100-1

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