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Observation of correlated excitations in bimolecular collisions

Abstract

Although collisions between atoms and molecules are largely understood, collisions between two molecules have proven much harder to study. In both experiment and theory, our ability to determine quantum-state-resolved bimolecular cross-sections lags behind their atom–molecule counterparts by decades. For many bimolecular systems, even rules of thumb—much less intuitive understanding—of scattering cross sections are lacking. Here, we report the measurement of state-to-state differential cross sections on the collision of state-selected and velocity-controlled nitric oxide (NO) radicals and oxygen (O2) molecules. Using velocity map imaging of the scattered NO radicals, the full product-pair correlations of rotational excitation that occurs in both collision partners from individual encounters are revealed. The correlated cross sections show surprisingly good agreement with quantum scattering calculations using ab initio NO−O2 potential energy surfaces. The observations show that the well-known energy-gap law that governs atom–molecule collisions does not generally apply to bimolecular excitation processes, and reveal a propensity rule for the vector correlation of product angular momenta.

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Fig. 1: Rotational energy level diagrams of NO and O2, and the Newton diagram for NO–O2 collisions.
Fig. 2: Experimental (Exp.) and simulated (Sim.) scattering images for the scattering processes NO (1/2f) + O2 (\({N}_{{{\rm{O}}}_{2}}=1\)) → NO (\({j}_{{\rm{N}}{\rm{O}}}^{{}^{<mml:mpadded xmlns:xlink="http://www.w3.org/1999/xlink" voffset="-4pt">{\boldsymbol{\text{'}}}</mml:mpadded>}}\)) + O2 (\({N}_{{{\rm{O}}}_{2}}^{<mml:mpadded xmlns:xlink="http://www.w3.org/1999/xlink" voffset="-1pt">\text{'}</mml:mpadded>}\)).
Fig. 3: Radial intensity distribution of the experimental (red curves) and simulated (blue curves) scattering images from Fig. 2.
Fig. 4: Analysis of the sum of angular momenta before and after the collision.

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References

  1. Kramer, K. H. & Bernstein, R. B. Focusing and orientation of symmetric-top molecules with the electric six-pole field. J. Chem. Phys. 42, 767–770 (1965).

    Article  CAS  Google Scholar 

  2. van de Meerakker, S. Y. T., Bethlem, H. L., Vanhaecke, N. & Meijer, G. Manipulation and control of molecular beams. Chem. Rev. 112, 4828–4878 (2012).

    Article  CAS  PubMed  Google Scholar 

  3. van de Meerakker, S. Y. T., Bethlem, H. L. & Meijer, G. Taming molecular beams. Nat. Phys. 4, 595–602 (2008).

    Google Scholar 

  4. Stolte, S. Aiming the molecular arrow. Nature 353, 391–392 (1991).

    Article  Google Scholar 

  5. Chandler, D. W. & Stolte, S. in Gas Phase Molecular Reaction and Photodissociation Dynamics (Lin, K. C. & Kleiber, P. D.) Ch. 1 (Transworld Research Network, Kerala, 2007).

    Google Scholar 

  6. Aoiz, F. J. et al. A new perspective: imaging the stereochemistry of molecular collisions. Phys. Chem. Chem. Phys. 17, 30210–30228 (2015).

    Article  CAS  PubMed  Google Scholar 

  7. Wang, F., Liu, K. & Rakitzis, T. P. Revealing the stereospecific chemistry of the reaction of Cl with aligned CHD3 (v 1=1). Nat. Chem. 4, 636 (2012).

    Article  CAS  PubMed  Google Scholar 

  8. Costen, M. L., Marinakis, S. & McKendrick, K. G. Do vectors point the way to understanding energy transfer in molecular collisions? Chem. Soc. Rev. 37, 732–743 (2008).

    Article  CAS  PubMed  Google Scholar 

  9. Brouard, M., Hornung, B. & Aoiz, F. J. Origin of collision-induced molecular orientation. Phys. Rev. Lett. 111, 183202 (2013).

    Article  CAS  PubMed  Google Scholar 

  10. Brouard, M., Chadwick, H., Eyles, C. J., Aoiz, F. J. & Kłos, J. The kjj′ vector correlation in inelastic and reactive scattering. J. Chem. Phys. 135, 084305 (2011).

    Article  CAS  PubMed  Google Scholar 

  11. Onvlee, J. et al. Imaging quantum stereodynamics through fraunhofer scattering of NO radicals with rare-gas atoms. Nat. Chem. 9, 226–233 (2017).

    Article  CAS  PubMed  Google Scholar 

  12. Chefdeville, S. et al. Appearance of low energy resonances in CO-para-H2 inelastic collisions. Phys. Rev. Lett. 109, 023201 (2012).

    Article  CAS  PubMed  Google Scholar 

  13. Kirste, M. et al. Quantum-state resolved bimolecular collisions of velocity-controlled OH with NO radicals. Science 338, 1060–1063 (2012).

    Article  CAS  PubMed  Google Scholar 

  14. Liu, K. Product pair correlation in bimolecular reactions. Phys. Chem. Chem. Phys. 9, 17–30 (2007).

    Article  CAS  PubMed  Google Scholar 

  15. Buck, U., Huisken, F., Maneke, G. & Schaefer, J. State resolved rotational excitation in HD+D2 collisions. ii. Angular dependence of 0→2 transitions. J. Chem. Phys. 78, 4430–4438 (1983).

    Article  CAS  Google Scholar 

  16. Townsend, D. et al. The roaming atom: straying from the reaction path in formaldehyde decomposition. Science 306, 1158–1161 (2004).

    Article  CAS  PubMed  Google Scholar 

  17. Hause, M. L., Herath, N., Zhu, R., Lin, M. C. & Suits, A. G. Roaming-mediated isomerization in the photodissociation of nitrobenzene. Nat. Chem. 3, 932–937 (2011).

    Article  CAS  PubMed  Google Scholar 

  18. Grubb, M. P. et al. No straight path: roaming in both ground- and excited-state photolytic channels of NO3 →NO+O2. Science 335, 1075–1078 (2012).

    Article  CAS  PubMed  Google Scholar 

  19. Zhang, Z. et al. Imaging the pair-correlated HNCO photodissociation: The NH(a1Δ)+CO(X1Σ+) channel. J. Phys. Chem. A 118, 2413–2418 (2014).

    Article  CAS  PubMed  Google Scholar 

  20. Lin, J. J., Zhou, J., Shiu, W. & Liu, K. State-specific correlation of coincident product pairs in the F+CD4 reaction. Science 300, 966–969 (2003).

    Article  CAS  PubMed  Google Scholar 

  21. Yan, S., Wu, Y.-T., Zhang, B., Yue, X.-F. & Liu, K. Do vibrational excitations of CHD3 preferentially promote reactivity toward the chlorine atom? Science 316, 1723–1726 (2007).

    Article  CAS  PubMed  Google Scholar 

  22. Zhang, W., Kawamata, H. & Liu, K. CH stretching excitation in the early barrier F+CHD3 reaction inhibits CH bond cleavage. Science 325, 303–306 (2009).

    Article  CAS  PubMed  Google Scholar 

  23. Wang, F., Lin, J.-S. & Liu, K. Steric control of the reaction of CH stretch–excited CHD3 with chlorine atom. Science 331, 900–903 (2011).

    Article  CAS  PubMed  Google Scholar 

  24. Wang, T. et al. Dynamical resonances accessible only by reagent vibrational excitation in the F+HD → HF+D reaction. Science 342, 1499–1502 (2013).

    Article  CAS  PubMed  Google Scholar 

  25. Yang, T. et al. Extremely short-lived reaction resonances in Cl+HD (v=1) → DCl+H due to chemical bond softening. Science 347, 60–63 (2015).

    Article  CAS  PubMed  Google Scholar 

  26. Brouard, M. et al. Angular distributions for the inelastic scattering of NO(X2Π) with O2(X3 \({{\rm{\Sigma }}}_{{\rm{g}}}^{-}\)). J. Chem. Phys. 146, 204304 (2017).

  27. Luxford, T. F. M., Sharples, T. R., McKendrick, K. G. & Costen, M. L. Pair-correlated stereodynamics for diatom-diatom rotational energy transfer: NO(A2Σ+)+N2. J. Chem. Phys. 147, 013912 (2017).

    Article  CAS  PubMed  Google Scholar 

  28. Gijsbertsen, A., Linnartz, H. & Stolte, S. Parity-dependent rotational rainbows in D2-NO and He-NO differential collision cross sections. J. Chem. Phys. 125, 133112 (2006).

    Article  CAS  PubMed  Google Scholar 

  29. Yang, C.-H., Sarma, G., Parker, D. H., ter Meulen, J. J. & Wiesenfeld, L. State-to-state differential and relative integral cross sections for rotationally inelastic scattering of H2O by hydrogen. J. Chem. Phys. 134, 204308 (2011).

    Article  CAS  PubMed  Google Scholar 

  30. Tkáč, O., Rusher, C. A., Greaves, S. J., Orr-Ewing, A. J. & Dagdigian, P. J. Differential and integral cross sections for the rotationally inelastic scattering of methyl radicals with H2 and D2. J. Chem. Phys. 140, 204318 (2014).

    Article  CAS  PubMed  Google Scholar 

  31. Tkáč, O. et al. Rotationally inelastic scattering of ND3 with H2 as a probe of the intermolecular potential energy surface. Mol. Phys. 113, 3925–3933 (2015).

    Article  CAS  Google Scholar 

  32. von Zastrow, A. et al. State-resolved diffraction oscillations imaged for inelastic collisions of NO radicals with He, Ne and Ar. Nat. Chem. 6, 216–221 (2014).

    Article  CAS  Google Scholar 

  33. Vogels, S. N. et al. Imaging resonances in low-energy NO-He inelastic collisions. Science 350, 787–790 (2015).

    Article  CAS  PubMed  Google Scholar 

  34. Bacon, J. A., Giese, C. F. & Gentry, W. R. State-to-state differential cross sections for rotationally inelastic collisions of NO (2Π1/2, j≤2.5) with CO (1Σ+) and O2 (3 \({{\rm{\Sigma }}}_{{\rm{g}}}^{-}\)) at a kinetic energy of 442 cm−1. J. Chem. Phys. 108, 3127–3133 (1998).

  35. Karman, T., van der Avoird, A. & Groenenboom, G. C. Communication: multiple-property-based diabatization for open-shell van der waals molecules. J. Chem. Phys. 144, 121101 (2016).

    Article  CAS  PubMed  Google Scholar 

  36. Onvlee, J., Vogels, S. N., von Zastrow, A., Parker, D. H. & van de Meerakker, S. Y. T. Molecular collisions coming into focus. Phys. Chem. Chem. Phys. 16, 15768–15779 (2014).

    Article  CAS  PubMed  Google Scholar 

  37. Yan, B. et al. A new high intensity and short-pulse molecular beam valve. Rev. Sci. Instrum. 84, 023102 (2013).

    Article  CAS  PubMed  Google Scholar 

  38. Townsend, D., Minitti, M. P. & Suits, A. G. Direct current slice imaging. Rev. Sci. Instrum. 74, 2530–2539 (2003).

    Article  CAS  Google Scholar 

  39. Even, U. Pulsed supersonic beams from high pressure source: Simulation results and experimental measurements. Adv. Chem. 2014, 1–11 (2014).

    Article  CAS  Google Scholar 

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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 program of the Netherlands Organization for Scientific Research (NWO). The expert technical support by N. Janssen, A. van Roij and E. Sweers is gratefully acknowledged.

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Contributions

The experiments were conceived by S.Y.T.v.d.M. The experiments were carried out by Z.G. with the help of S.N.V. Data analysis and simulations were performed by Z.G. Potential energy surfaces were calculated by T.K., A.v.d.A. and G.C.G. Scattering calculations were performed by T.K. and M.B. Analysis of quantum entanglement was performed by T.K. All authors were involved in the interpretation of the data, discussed the results, and commented on the manuscript. The paper was written by Z.G., T.K. and S.Y.T.v.d.M. with contributions from all authors.

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

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Supplementary Information

Supplementary Methods, Analysis and Calculations; Supplementary Figs. 1–14

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Gao, Z., Karman, T., Vogels, S.N. et al. Observation of correlated excitations in bimolecular collisions. Nature Chem 10, 469–473 (2018). https://doi.org/10.1038/s41557-018-0004-0

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