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Scattering resonances in bimolecular collisions between NO radicals and H2 challenge the theoretical gold standard

Nature Chemistry volume 10, pages 435–440 (2018)Cite this article

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Abstract

Over the last 25 years, the formalism known as coupled-cluster (CC) theory has emerged as the method of choice for the ab initio calculation of intermolecular interaction potentials. The implementation known as CCSD(T) is often referred to as the gold standard in quantum chemistry. It gives excellent agreement with experimental observations for a variety of energy-transfer processes in molecular collisions, and it is used to calibrate density functional theory. Here, we present measurements of low-energy collisions between NO radicals and H2 molecules with a resolution that challenges the most sophisticated quantum chemistry calculations at the CCSD(T) level. Using hitherto-unexplored anti-seeding techniques to reduce the collision energy in a crossed-beam inelastic-scattering experiment, a resonance structure near 14 cm−1 is clearly resolved in the state-to-state integral cross-section, and a unique resonance fingerprint is observed in the corresponding differential cross-section. This resonance structure discriminates between two NO–H2 potentials calculated at the CCSD(T) level and pushes the required accuracy beyond the gold standard.

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Fig. 1: Illustration of two potentials V (red and blue) as a function of internuclear distance R, which differ slightly in well depth.
Fig. 2: Experimental overview and ion image data.
Fig. 3: Collision energy dependence of the partial ICS for scattering angles θ between 90° and 180°.
Fig. 4: Comparison between total and partial ICSs in the resonance region.
Fig. 5: Experimental and simulated ion images as a function of collision energy Ecol.

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Acknowledgements

The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement 335646 MOLBIL. This work is part of the research programme of the Netherlands Organization for Scientific Research (NWO). J.K. acknowledges financial support through US NSF grant no. CHE-1565872 to M.H. Alexander. The authors thank C. Berkhout, N. Janssen and A. van Roij for expert technical support, and Q. Ma for help in fitting the F12 potential.

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Author notes

  1. Jolijn Onvlee

    Present address: Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron DESY, Hamburg, Germany

  2. These authors contributed equally: Sjoerd N. Vogels and Tijs Karman.

Authors and Affiliations

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

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

  2. Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, USA

    Jacek Kłos

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  1. Sjoerd N. Vogels
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Contributions

The experiments were conceived by S.Y.T.v.d.M. Experiments were carried out by S.N.V. Data analysis and simulations were performed by S.N.V. and J.O. Potential energy surfaces for NO–H2 were calculated by T.K., A.v.d.A., G.C.G. and J.K. Scattering calculations were performed by T.K., J.K., J.O. and M.B. The partial wave analysis was performed by M.B. All authors were involved in interpretation of the data, discussed the results, and commented on the manuscript. The paper was written by S.N.V. and S.Y.T.v.d.M. with contributions from all authors.

Corresponding authors

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

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Supplementary Methods and analysis, Supplementary Figs. 1–7 and Supplementary Tables 1 and 2

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Vogels, S.N., Karman, T., Kłos, J. et al. Scattering resonances in bimolecular collisions between NO radicals and H2 challenge the theoretical gold standard. Nature Chem 10, 435–440 (2018). https://doi.org/10.1038/s41557-018-0001-3

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