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Mapping partial wave dynamics in scattering resonances by rotational de-excitation collisions

Nature Chemistry volume 14, pages 538–544 (2022)Cite this article

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Abstract

One of the most important parameters in a collision is the ‘miss distance’ or impact parameter, which in quantum mechanics is described by quantized partial waves. Usually, the collision outcome is the result of unavoidable averaging over many partial waves. Here we present a study of low-energy NO–He collisions that enables us to probe how individual partial waves evolve during the collision. By tuning the collision energies to scattering resonances between 0.4 and 6 cm−1, the initial conditions are characterized by a limited set of partial waves. By preparing NO in a rotationally excited state before the collision and by studying rotational de-excitation collisions, we were able to add one quantum of angular momentum to the system and trace how it evolves. Distinct fingerprints in the differential cross-sections yield a comprehensive picture of the partial wave dynamics during the scattering process. Exploiting the principle of detailed balance, we show that rotational de-excitation collisions probe time-reversed excitation processes with superior energy and angular resolution.

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Fig. 1: Collision energy dependence of the ICS and energy level diagram of the involved molecular states.
Fig. 2: Partial-wave contributions to the cross-section at several probed collision energies.
Fig. 3: Experimental and simulated ion images at selected collision energies.
Fig. 4: Experimental and simulated ion images for two inelastic scattering processes subject to the detailed balance principle.

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Data availability

All data are available online at DANS: https://doi.org/10.17026/dans-x8q-pcuk.

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Acknowledgements

This work is part of the research programme of the Netherlands Organization for Scientific Research. S.Y.T.v.d.M. acknowledges support from the European Research Council under the European Union’s Seventh Framework Program (FP7/2007-2013/ERC grant agreement no. 335646 MOLBIL) and from the European Research Council under the European Union’s Horizon 2020 Research and Innovation Program (grant agreement no. 817947 FICOMOL). We thank N. Janssen and A. van Roij for expert technical support. We thank F. J. M. Harren for stimulating discussions regarding the optical excitation of NO using a quantum cascade laser. We thank T. Karman for fruitful discussions and for critically reading the manuscript.

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Author notes

  1. Tim de Jongh

    Present address: Laboratoire Kastler Brossel, ENS-Université PSL, CNRS, Sorbonne Université, Collége de France, Paris, France

  2. Quan Shuai

    Present address: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

  3. These authors contributed equally: Tim de Jongh, Quan Shuai.

Authors and Affiliations

  1. Institute for Molecules and Materials, Radboud University, Nijmegen, The Netherlands

    Tim de Jongh, Quan Shuai, Grite L. Abma, Stach Kuijpers, Matthieu Besemer, Ad van der Avoird, Gerrit C. Groenenboom & Sebastiaan Y. T. van de Meerakker

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Contributions

The project was conceived by S.Y.T.v.d.M. The experiments were carried out by T.d.J., Q.S. and S.K. Methods to rovibrationally excite NO using a quantum cascade laser were developed by G.A. and Q.S. Data analysis and simulations were performed by T.d.J. Theoretical calculations were performed by M.B., A.v.d.A. and G.C.G. The manuscript was written by T.d.J. and S.Y.T.v.d.M. with contributions from all authors. All authors were involved in the interpretation of the data and the preparation of the manuscript.

Corresponding authors

Correspondence to Gerrit C. Groenenboom or Sebastiaan Y. T. van de Meerakker.

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The authors declare no competing interests.

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

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Supplementary Figs. 1–11, Tables 1–3, Methods and Results.

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de Jongh, T., Shuai, Q., Abma, G.L. et al. Mapping partial wave dynamics in scattering resonances by rotational de-excitation collisions. Nat. Chem. 14, 538–544 (2022). https://doi.org/10.1038/s41557-022-00896-2

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