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Fermi-phase-induced interference in the reaction between Cl and vibrationally excited CH3D

Nature Chemistry volume 14, pages 545–549 (2022)Cite this article

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Abstract

Mode selectivity is a well-established concept in chemical dynamics. A polyatomic molecule possesses multiple vibrational modes and the mechanical couplings between them can result in complicated anharmonic motions that defy a simple oscillatory description. A prototypical example of this is Fermi-coupled vibration, in which an energy-split eigenstate executes coherent nuclear motion that is comprised of the constituent normal modes with distinctive phases. Will this vibrational phase affect chemical reactivity? How can this phase effect be disentangled from more classical amplitude effects? Here, to address these questions, we study the reaction of Cl with a pair of Fermi states of CH3D(v1-I and v1-II). We find that the reactivity ratio of (v1-I)/(v1-II) in forming the CH2D(v = 0) + HCl(v) products deviates significantly from that permitted by the conventional reactivity-borrowing framework. Based on a proposed metric, this discrepancy can only be explained when the scattering interferences mediated by the CH3D vibrational phases are explicitly considered, which expands the concept of vibrational control of chemical reactivity into the quantum regime.

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Fig. 1: Schematic energies of the reactions.
Fig. 2: Ec dependencies of the product speed distributions and relative reactivity of Fermi-coupled reagents.
Fig. 3: Illustration of how the corner-turning region of PES affects the mixing angle of a pair of Fermi-coupled reagents and thereby the reactivity.

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Data availability

Datasets are available at https://doi.org/10.5281/zenodo.6119459 (ref. 38) and as Supplementary Data 1.

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Acknowledgements

We thank S. I. Mondal for assisting with some imaging acquisitions; S. Liu for providing the PES shown in Fig. 3a; H. Guo, D. H. Zhang, S. Liu and J. L. Kuo for helpful discussions. K.L. is indebted to A. Stolow for a stimulating discussion on the H + CO2 reaction at a 2014 meeting in St Petersburg, which eventually led to this project. This work was supported by Minister of Science and Technology of Taiwan (MOST-105-2113-M-001-019) and Academia Sinica (2318-1030200). H.P. also acknowledges support from the National Natural Science Foundation of China (grant 22003024), the Guangdong Introduced Innovative R&D Team Project (grant 2019ZT08L455) and the State Key Laboratory of Molecular Reaction Dynamics (grant SKLMRD-K202119). The funders had no role in study design, data collection and analysis, decision to publish or preparation of the manuscript.

Author information

Authors and Affiliations

  1. Southern University of Science and Technology, Shenzhen, P. R. China

    Huilin Pan

  2. Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan

    Huilin Pan & Kopin Liu

  3. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, CAS, Dalian, P. R. China

    Kopin Liu

  4. Aerosol Science Research Center, National Sun Yat-sen University, Kaohsiung, Taiwan

    Kopin Liu

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Contributions

K.L. conceived and supervised the project. H.P. performed the experiment and analysed the data. Both authors discussed the results and contributed to the interpretations. K.L. wrote the manuscript with input from H.P.

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Correspondence to Huilin Pan or Kopin Liu.

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The authors declare no competing interests.

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Nature Chemistry thanks Hongwei Song and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1

Schematics illustrating the crossed molecular-beam, time-sliced product imaging setup.

Extended Data Fig. 2 Raw images of the probed CH2D(00) products.

Top two rows summarize the raw difference images (with the ground-state reaction signal subtracted) of the CH2D products in the reactions of a pair of Fermi-coupled CH3D(v1-I and v1-II) with Cl atoms at four Ec’s. The bottom row displays the corresponding ground-state reaction images. Images at 10 kcal mol−1 are taken from ref. 22 for completeness. On energetic grounds, the ring-like features in the images were assigned to the (vCH2D, vHCl)s/g product pairs; the subscript “s” or “g” denotes the stretch-excited or ground-state reaction. The collisional energies (in kcal mol−1) are indicated at the top.

Extended Data Fig. 3 Comparisons of the dσ/du distributions of the CH2D(00) + HCl(v = 0, 1) channels in the reactions of Cl atoms with two Fermi-dyad reagents, CH3D(v1-I and v1-II).

At each Ec (indicated at the upper-left corner, in kcal mol−1), two distributions are normalized by the slow-speed components for ready comparison. The vibrational branching of the HCl(v) co-products evolves from a hotter one at low Ec to a colder one with increasing Ec. Also note the nearly identical distributions in reactions with the v1-I and v1-II reagents for Ec ≤ 5.2 kcal mol−1 and slight differences at higher Ec. The product pair is labelled as (vCH2D, vHCl)s with the subscript “s” for the stretch-excited reaction.

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Supplementary Data 1

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Pan, H., Liu, K. Fermi-phase-induced interference in the reaction between Cl and vibrationally excited CH3D. Nat. Chem. 14, 545–549 (2022). https://doi.org/10.1038/s41557-022-00914-3

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