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Imaging quantum stereodynamics through Fraunhofer scattering of NO radicals with rare-gas atoms

Nature Chemistry volume 9, pages 226–233 (2017)Cite this article

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Abstract

Stereodynamics describes how the vector properties of molecules, such as the directions in which they move and the axes about which they rotate, affect the probabilities (or cross-sections) of specific processes or transitions that occur on collision. The main aspects of stereodynamics in inelastic atom–molecule collisions can often be understood from classical considerations, in which the particles are represented by billiard-ball-like hard objects. In a quantum picture, however, the collision is described in terms of matter waves, which can also scatter into the region of the geometrical shadow of the object and reveal detailed information on the pure quantum-mechanical contribution to the stereodynamics. Here we present measurements of irregular diffraction patterns for NO radicals colliding with rare-gas atoms that can be explained by the analytical Fraunhofer model. They reveal a hitherto overlooked dependence on (or ‘propensity rule’ for) the magnetic quantum number m of the molecules, and a previously unrecognized type of quantum stereodynamics that has no classical analogue or interpretation.

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Figure 1: Illustration of the classical and wave-like regimes that we use to describe stereodynamics in molecular collisions.
Figure 2: DCSs for NO radicals colliding with various rare-gas atoms resulting from the QMCC calculations (red solid curve) and the Fraunhofer model (black dashed curve).
Figure 3: Angular distributions and DCSs for NO radicals colliding with various rare-gas atoms.
Figure 4: The m,m′-resolved DCSs obtained from the QMCC calculations in the scattering frame.
Figure 5: Illustration of the stereodynamics for NO + Ar, j′ = 11/2,e collisions, for which κ = 6, leading to the irregular diffraction peak.

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Acknowledgements

The research leading to these results has received funding from the European Research Council (ERC) under the European Union's Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement 335646 MOLBIL. This work is part of the research program of the Foundation for Fundamental Research on Matter (FOM), which is financially supported by the Netherlands Organization for Scientific Research (NWO). S.Y.T.v.d.M. acknowledges support from NWO via a VIDI and a TOP grant. The support of the UK EPSRC (to M.B. via Programme Grant EP/L005913/1) is gratefully acknowledged. S.D.S.G and M.B thank Cambio Ltd and P. Dean for generous support. The authors thank M. Lemeshko for carefully reading the manuscript and for valuable suggestions. Moreover, we thank L. Gerritsen, C. Berkhout, P. Claus, N. Janssen and A. van Roij for expert technical support.

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  1. Thomas Auth

    Present address: Present address: Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 4, Göttingen 37077, Germany,

Authors and Affiliations

  1. Institute for Molecules and Materials, Radboud University, Heijendaalseweg 135, Nijmegen, 6525 AJ, the Netherlands

    Jolijn Onvlee, Sjoerd N. Vogels, Tijs Karman, Ad van der Avoird, Gerrit C. Groenenboom & Sebastiaan Y. T. van de Meerakker

  2. Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK

    Sean D. S. Gordon, Thomas Auth, Bethan Nichols & Mark Brouard

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Contributions

The project was conceived by S.Y.T.v.d.M. and M.B. The experiments were carried out by S.N.V. Data analysis and simulations were performed by J.O. and S.N.V. Scattering calculations were performed by J.O. using a scattering program developed by G.C.G. and A.v.d.A. The interpretation of the data using the Fraunhofer model was performed by J.O., A.v.d.A., G.C.G. and S.Y.T.v.d.M. with input from S.D.S.G., T.A., T.K., B.N. and M.B. The explanation of vector correlations based on the Fraunhofer model and the Huygens principle was developed by G.C.G., A.v.d.A., T.K., J.O. and S.Y.T.v.d.M. The ESA calculations were performed by T.K. The kinematic apse model calculations were performed by S.D.S.G. The paper was written by J.O. and S.Y.T.v.d.M. with contributions from all the authors.

Corresponding authors

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

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Onvlee, J., Gordon, S., Vogels, S. et al. Imaging quantum stereodynamics through Fraunhofer scattering of NO radicals with rare-gas atoms. Nature Chem 9, 226–233 (2017). https://doi.org/10.1038/nchem.2640

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