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Non-intuitive rotational reorientation in collisions of NO(A 2Σ+) with Ne from direct measurement of a four-vector correlation

Nature Chemistry volume 10, pages 1148–1153 (2018)Cite this article

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Abstract

Stereodynamic descriptions of molecular collisions concern the angular correlations that exist between vector properties of the motion of the participating species, including their velocities and rotational angular momenta. Measurements of vector correlations provide a unique view of the forces acting during collisions, and are a stringent test of electronic-structure calculations of molecular interactions. Here, we present direct measurement of the four-vector correlation between initial and final relative velocities and rotational angular momenta in a molecular collision. This property, which quantifies the extent to which a molecule retains a memory of its initial sense of rotation, or handedness, as a function of scattering angle, yields insight into the dynamics of a molecular collision. We report non-intuitive changes in the handedness for specific states and scattering angles, reproduced by classical and quantum scattering calculations. Comparison to calculations on different ab initio potential energy surfaces demonstrates this measurement’s exquisite sensitivity to the underlying intermolecular forces.

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Fig. 1: Illustration of two possible correlations between the initial and final rotational angular momentum, resolved at different scattering angles.
Fig. 2: Schematic of the experimental set-up and Newton diagram showing the directions of the velocity vectors describing the colliders before collision.
Fig. 3: Velocity map images used to measure the k–j–k′–j′ correlation.
Fig. 4: Measured and calculated values of C(θ) for each N′ final state, revealing the variation of the orientation transfer with scattering angle.

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Acknowledgements

This work was supported by the UK EPSRC via grants EP/J017973/01 and EP/P001459/1. J.G.L. thanks the EPSRC for provision of a DTP studentship (EP/N509474/1). T.F.M.L. acknowledges Heriot-Watt University for a James Watt PhD scholarship. P.G.J. and F.J.A. acknowledge funding by the Spanish Ministry of Science and Innovation (grant MINECO/FEDER-CTQ2015-65033-P) and E. Verdasco for support with calculations. P.G.J. acknowledges funding by Fundación Salamanca City of Culture and Knowledge. The work of D.W.C. was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under grant 2019 SNL 17014098. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the US Department of Energy’s National Nuclear Security Administration under contract DE-NA-0003525. The authors also acknowledge the assistance of P.J. Dagdigian, J. Kłos and M.H. Alexander in performing quantum scattering calculations.

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Authors and Affiliations

  1. Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, UK

    Thomas R. Sharples, Joseph G. Leng, Thomas F. M. Luxford, Kenneth. G. McKendrick & Matthew L. Costen

  2. Departamento de Química Física Aplicada, Facultad de Ciencias, Universidad Autónoma de Madrid, Madrid, Spain

    Pablo G. Jambrina

  3. Departamento de Química Física, Facultad de Ciencias Químicas, Universidad de Salamanca, Salamanca, Spain

    Pablo G. Jambrina

  4. Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Madrid, Spain

    F. Javier Aoiz

  5. Combustion Research Facility, Sandia National Laboratory, Livermore, CA, USA

    David W. Chandler

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Contributions

The research project was conceived and supervised by M.L.C. Experiments were carried out by T.R.S., J.G.L., T.F.M.L. and D.W.C. Data analysis was performed by T.R.S. and J.G.L. Quantum scattering calculations were carried out by T.R.S. Quasi-classical trajectory calculations were performed by P.G.J. and F.J.A. Kinematic apse calculations were performed by M.L.C. and T.R.S. The results were interpreted by T.R.S., P.G.J., F.J.A., D.W.C., K.G.M. and M.L.C. The manuscript was written by T.R.S. with contributions from all authors.

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Correspondence to David W. Chandler or Matthew L. Costen.

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Supplementary information

Supplementary Information

Supplementary Experimental Methods, Supplementary Theoretical Methods, Supplementary Analysis, Supplementary Figures 1–7, Supplementary Table 1

Supplementary Video 1

Animated trajectory on the CF PES leading to N' = 5 (θ = 60°) for which a reversal in the handedness of the NO rotation leads to a change in the direction in which the rotational angular momentum points relative to k. The three atoms are shown as spheres (Ar, yellow; N, blue; O, red) while the rotational angular momentum is shown as a grey line.

Supplementary Video 2

Animated trajectory on the CF PES leading to N' = 5 (θ = 60°) for which a small change in the angle between j and j′ leads to a change in the direction in which the rotational angular momentum points relative to k. The three atoms are shown as spheres (Ar: yellow, N: blue, O: red) while the rotational angular momentum is shown as a grey line.

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Sharples, T.R., Leng, J.G., Luxford, T.F.M. et al. Non-intuitive rotational reorientation in collisions of NO(A 2Σ+) with Ne from direct measurement of a four-vector correlation. Nature Chem 10, 1148–1153 (2018). https://doi.org/10.1038/s41557-018-0121-9

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