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Feshbach resonances in the exit channel of the F + CH3OH → HF + CH3O reaction observed using transition-state spectroscopy

Nature Chemistry volume 9, pages 950–955 (2017)Cite this article

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Abstract

The transition state governs how chemical bonds form and cleave during a chemical reaction and its direct characterization is a long-standing challenge in physical chemistry. Transition state spectroscopy experiments based on negative-ion photodetachment provide a direct probe of the vibrational structure and metastable resonances that are characteristic of the reactive surface. Dynamical resonances are extremely sensitive to the topography of the reactive surface and provide an exceptional point of comparison with theory. Here we study the seven-atom F + CH3OH → HF + CH3O reaction using slow photoelectron velocity-map imaging spectroscopy of cryocooled CH3OHF− anions. These measurements reveal spectral features associated with a manifold of vibrational Feshbach resonances and bound states supported by the post-transition state potential well. Quantum dynamical calculations yield excellent agreement with the experimental results, allow the assignment of spectral structure and demonstrate that the key dynamics of complex bimolecular reactions can be captured with a relatively simple theoretical framework.

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Figure 1: Schematic energy diagram for the photodetachment of the CH3OHF− anion to the neutral F + CH3OH → HF + CH3O reactive PES.
Figure 2: Experimental and theoretical photodetachment spectra of CH3OHF− and CH3ODF− showing transitions to resonances in the F + CH3OH → HF + CH3O product well.
Figure 3: Cuts of the CH3OHF− anion vibrational ground-state wavefunction and representative F + CH3OH → HF + CH3O resonance wavefunctions.

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Acknowledgements

This work is funded by the US Air Force Office of Scientific Research (Grants no. FA9550-16-1-0097 to D.M.N. and no. FA9550-15-1-0305 to H.G.), and the National Natural Science Foundation of China (Contracts no. 21573027 to J.L. and no. 91441107 to J.M.). M.L.W. thanks the National Science Foundation for a graduate research fellowship.

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Authors and Affiliations

  1. Department of Chemistry, University of California, Berkeley, 94720, California, USA

    Marissa L. Weichman, Jessalyn A. DeVine, Mark C. Babin & Daniel M. Neumark

  2. School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 401331, China

    Jun Li

  3. Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, 610065, Sichuan, China

    Lifen Guo & Jianyi Ma

  4. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, 87131, New Mexico, USA

    Hua Guo

  5. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, 94720, California, USA

    Daniel M. Neumark

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Contributions

The experimental research was conceived and supervised by D.M.N. The experiments were carried out by M.L.W., J.A.D. and M.C.B. Experimental data analysis and interpretation was performed by M.L.W. Theoretical calculations were conceived by J.L., J.M. and H.G. and performed by J.L., L.G. and J.M. The paper was written by M.L.W., with the theoretical sections contributed by J.L., J.M. and H.G. All of the authors contributed to discussions about the results and manuscript.

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Correspondence to Jun Li or Daniel M. Neumark.

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Weichman, M., DeVine, J., Babin, M. et al. Feshbach resonances in the exit channel of the F + CH3OH → HF + CH3O reaction observed using transition-state spectroscopy. Nature Chem 9, 950–955 (2017). https://doi.org/10.1038/nchem.2804

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