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Cold quantum-controlled rotationally inelastic scattering of HD with H2 and D2 reveals collisional partner reorientation

Abstract

Molecular interactions are best probed by scattering experiments. Interpretation of these studies has been limited by lack of control over the quantum states of the incoming collision partners. We report here the rotationally inelastic collisions of quantum-state prepared deuterium hydride (HD) with H2 and D2 using a method that provides an improved control over the input states. HD was coexpanded with its partner in a single supersonic beam, which reduced the collision temperature to 0–5 K, and thereby restricted the involved incoming partial waves to s and p. By preparing HD with its bond axis preferentially aligned parallel and perpendicular to the relative velocity of the colliding partners, we observed that the rotational relaxation of HD depends strongly on the initial bond-axis orientation. We developed a partial-wave analysis that conclusively demonstrates that the scattering mechanism involves the exchange of internal angular momentum between the colliding partners. The striking differences between H2/HD and D2/HD scattering suggest the presence of anisotropically sensitive resonances.

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Fig. 1: Relative-speed and energy distributions.
Fig. 2: Two different collision geometries.
Fig. 3: D2/HD mixed-beam scattering.
Fig. 4: H2/HD mixed-beam scattering.

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References

  1. Blatt, J. M. & Biedenharn, L. C. The angular distribution of scattering and reaction cross sections. Rev. Mod. Phys. 24, 258–272 (1952).

    Article  CAS  Google Scholar 

  2. Arthurs, A. M. & Dalgarno, A. The theory of scattering by a rigid rotator. Proc. R. Soc. A 256, 540–551 (1960).

    Article  Google Scholar 

  3. Warren, W. S., Rabitz, H. & Dahleh, M. Coherent control of quantum dynamics: the dream is alive. Science 259, 1581–1589 (1993).

    Article  CAS  Google Scholar 

  4. Zare, R. N. Laser control of chemical reactions. Science 279, 1875–1879 (1998).

    Article  CAS  Google Scholar 

  5. PanH., Wang, F,. Czakó, G. & Liu, K. Direct mapping of the angle-dependent barrier to reaction for Cl + CHD3 using polarized scattering data. Nat. Chem. 9, 1175–1180 (2017).

    Article  CAS  Google Scholar 

  6. Smith, G. P. & Zare, R. N. Angular distribution of product internal states using laser fluorescence detection: the Ba + KCl reaction. J. Chem. Phys. 64, 2632–2640 (1976).

    Article  CAS  Google Scholar 

  7. 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  Google Scholar 

  8. Bartlett, N. C.-M. et al. Differential cross sections for H + D2 → HD(v′ = 2, j′ = 0,3,6,9) + D at center-of-mass collision energies of 1.25, 1.61, and 1.97 eV. Phys. Chem. Chem. Phys. 13, 8175–8179 (2011).

    Article  CAS  Google Scholar 

  9. Stuhl, B. K., Hummon, M. T. & Ye, J. Cold state-selected molecular collisions and reactions. Annu. Rev. Phys. Chem. 65, 501–518 (2014).

    Article  CAS  Google Scholar 

  10. Naulin, C. & Costes, M. Experimental search for scattering resonances in near cold molecular collisions. Int. Rev. Phys. Chem. 33, 427–446 (2014).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  12. Loesch, H. J. Orientation and alignment in reactive beam collisions: recent progress. Annu. Rev. Phys. Chem. 46, 555–594 (1995).

    Article  CAS  Google Scholar 

  13. Jones, E. M. & Brooks, P. R. Focusing and orienting asymmetric-top molecules in molecular beams. J. Chem. Phys. 53, 55–58 (1970).

    Article  CAS  Google Scholar 

  14. Loesch, H. J. & Remscheid, A. Brute force in molecular reaction dynamics: a novel technique for measuring steric effects. J. Chem. Phys. 93, 4779 (1990).

    Article  CAS  Google Scholar 

  15. van Leuken, J. J., van Amerom, F. H. W., Bulthuis, J., Snijders, J. G. & Stolte, S. Parity-resolved rotationally inelastic collisions of hexapole state-selected NO (2Π1/2, J = 0.5) with Ar. J. Phys. Chem. 99, 15573–15579 (1995).

    Article  Google Scholar 

  16. Brouard, M. et al. Fully quantum state-resolved inelastic scattering of NO(X) + Kr: differential cross sections and product rotational alignment. J. Chem. Phys. 141, 164306 (2014).

    Article  CAS  Google Scholar 

  17. Watanabe, D., Ohoyama, H., Matsumura, T. & Kasai, T. Effect of mutual configuration between molecular orientation and atomic orientation in the oriented Ar + oriented CF3H reaction. Phys. Rev. Lett. 99, 1–4 (2007).

    Google Scholar 

  18. Brouard, M., Parker, D. H. & van de Meerakker, S. Y. T. Taming molecular collisions using electric and magnetic fields. Chem. Soc. Rev. 43, 7279–7294 (2014).

    Article  CAS  Google Scholar 

  19. Rohlfing, E. A., Chandler, D. W. & Parker, D. H. Direct measurement of rotational energy transfer rate constants for HCl (v = 1). J. Chem. Phys. 87, 5229–5237 (1987).

    Article  CAS  Google Scholar 

  20. Dittmann, P. et al. The effect of vibrational excitation (3 ≤ v′ ≤ 19) on the reaction Na2 (v′) + Cl → NaCl + Na. J. Chem. Phys. 97, 9472 (1992).

    Article  CAS  Google Scholar 

  21. Liu, K. Perspective: vibrational-induced steric effects in bimolecular reactions. J. Chem. Phys. 142, 80901 (2015).

    Article  Google Scholar 

  22. Palla, F., Galli, D. & Silk, J. Deuterium in the universe. Astrophys. J. 451, 44–50 (1995).

    Article  CAS  Google Scholar 

  23. Dong, W., Mukherjee, N. & Zare, R. N. Optical preparation of H2 rovibrational levels with almost complete population transfer. J. Chem. Phys. 139, 74204 (2013).

    Article  Google Scholar 

  24. Mukherjee, N., Dong, W. & Zare, R. N. Coherent superposition of M-states in a single rovibrational level of H2 by Stark-induced adiabatic Raman passage. J. Chem. Phys. 140, 74201 (2014).

    Article  Google Scholar 

  25. Weck, P. F. & Balakrishnan, N. Importance of long-range interactions in chemical reactions at cold and ultracold temperatures. Int. Rev. Phys. Chem. 25, 283–311 (2006).

    Article  CAS  Google Scholar 

  26. Quéméner, G, Balakrishnan, N. & Dalgamo, A. in Stwalley, W. C., Krems, R. V. & Friedrich, B. (eds) Cold Molecules: Theory, Experiment, Applications 69–124 (CRC, Boca Raton, 2009)..

  27. Krems, R. V. Cold controlled chemistry. Phys. Chem. Chem. Phys. 10, 4079–4092 (2008).

    Article  CAS  Google Scholar 

  28. de Miranda, M. H. G. et al. Controlling the quantum stereodynamics of ultracold bimolecular reactions. Nat. Phys. 7, 502–507 (2011).

    Article  Google Scholar 

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

    Article  Google Scholar 

  30. Rowe, B. R. & Marquette, J. B. CRESU studies of ion/molecule reactions. Int. J. Mass Spectrom. Ion. Process 80, 239–254 (1987).

    Article  CAS  Google Scholar 

  31. Shagam, Y. et al. Molecular hydrogen interacts more strongly when rotationally excited at low temperatures leading to faster reactions. Nat. Chem. 7, 921–926 (2015).

    Article  CAS  Google Scholar 

  32. Chefdeville, S. et al. Observation of partial wave resonances in low-energy O2–H2 inelastic collisions. Science 341, 1094–1096 (2013).

    Article  CAS  Google Scholar 

  33. Perreault, W. E., Mukherjee, N. & Zare, R. N. Quantum control of molecular collisions at 1 kelvin. Science 358, 356–359 (2017).

    Article  CAS  Google Scholar 

  34. Amarasinghe, C. & Suits, A. G. Intrabeam scattering for ultracold collisions. J. Phys. Chem. Lett. 8, 5153–5159 (2017).

    Article  CAS  Google Scholar 

  35. Perreault, W. E., Mukherjee, N. & Zare, R. N. Angular and internal state distributions of H2 + generated by (2 + 1) resonance enhanced multiphoton ionization of H2 using time-of-flight mass spectrometry. J. Chem. Phys. 144, 214201 (2016).

    Article  Google Scholar 

  36. Perreault, W. E., Mukherjee, N. & Zare, R. N. Preparation of a selected high vibrational energy level of isolated molecules. J. Chem. Phys. 145, 154203 (2016).

    Article  Google Scholar 

  37. Buck, U., Huisken, F., Maneke, G. & Schaefer, J. State resolved rotational excitation in HD + D2 collisions. I. Angular dependence of 0→2 transitions. J. Chem. Phys. 74, 535–544 (1981).

    Article  CAS  Google Scholar 

  38. Buck, U. Rotationally inelastic scattering of hydrogen molecules and the non-spherical interaction. Faraday Discuss. Chem. Soc. 73, 187–203 (1982).

    Article  Google Scholar 

  39. Schaefer, J. Rotational integral cross sections and rate coeffients of HD scattered by He and H2. Astron. Astrophys. Suppl. Ser. 85, 1101–1125 (1990).

    CAS  Google Scholar 

  40. Lee, T.-G. et al. State-to-state rotational transitions in H2 + H2 collisions at low temperatures. J. Chem. Phys. 125, 114302 (2006).

    Article  Google Scholar 

  41. Lavert-Ofir, E. et al. Observation of the isotope effect in sub-kelvin reactions. Nat. Chem. 6, 332–335 (2014).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work has been supported by the US Army Research Office under ARO Grant No. W911NF-16-1-1061 and MURI Grant No. W911NF-12-1-0476.

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Contributions

All authors conceived of this study. W.E.P. and N.M. carried out the experimental work. N.M. developed the partial-wave analysis used to interpret the data. All the authors wrote the paper.

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Correspondence to Nandini Mukherjee or Richard N. Zare.

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The authors declare no competing interests.

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Supplementary Information

Supplementary Results and Analysis, Supplementary Tables 1–9

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Perreault, W.E., Mukherjee, N. & Zare, R.N. Cold quantum-controlled rotationally inelastic scattering of HD with H2 and D2 reveals collisional partner reorientation. Nature Chem 10, 561–567 (2018). https://doi.org/10.1038/s41557-018-0028-5

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