Enhanced reactivity of fluorine with para-hydrogen in cold interstellar clouds by resonance-induced quantum tunnelling

Abstract

Chemical reactions are important in the evolution of low-temperature interstellar clouds, where the quantum tunnelling effect becomes significant. The F + para-H2 → HF + H reaction, which has a significant barrier of 1.8 kcal mol−1, is an important source of HF in interstellar clouds; however, the dynamics of this quantum-tunnelling-induced reactivity at low temperature is unknown. Here, we show that this quantum tunnelling is caused by a post-barrier resonance state. Quantum-state-resolved crossed-beam scattering measurements reveal that this resonance state has a collision energy of ~5 meV and a lifetime of ~80 fs, which are in excellent agreement with a recent anion photoelectron spectroscopic study. Accurate quantum reactive scattering calculations on the new iCSZ-LWAL potential energy surfaces provides a detailed explanation of the experimental results. The reaction rate for this system was also theoretically determined accurately at temperatures as low as 1 K.

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Fig. 1: TOF spectra of the H-atom product from the F + H2(v = 0, j = 0) → HF(v′) + H reaction at 180° in the centre-of-mass frame.
Fig. 2: QSSBSS of the F + H2(v = 0, j = 0) → HF(v′ = 2) + H reaction and photodetachment spectra of p-FH2.
Fig. 3: Three-dimensional product contour plots as a function of product velocity for the F + H2(v = 0, j = 0) → HF + H reaction.
Fig. 4: Schematic explaining the roles of the two resonances states (003) and (103) in the product channel in the reaction of F + H2(j = 0) and F + H2(j = 1).
Fig. 5: Calculated reaction rate constants.
Fig. 6: Calculated reaction rate constants.

Data availability

Data supporting the findings of this study are available from the corresponding authors on request.

Code availability

The accurate iCSZ and iCSZ-LWAL PESs developed in this work are available from the corresponding authors on request.

References

  1. 1.

    Bell, R. P. The Tunnel Effect in Chemistry (Chapman & Hall, London, 1980).

  2. 2.

    Zuev, P. S. et al. Carbon tunnelling from a single quantum state. Science 299, 867–870 (2003).

    CAS  Article  Google Scholar 

  3. 3.

    Fleming, G. R., Scholes, G. D. & Cheng, Y. C. Quantum effects in biology. Procedia Chem. 3, 38–57 (2011).

    CAS  Article  Google Scholar 

  4. 4.

    Jankunas, J. & Osterwalder, A. Cold and controlled molecular beams: production and application. Annu. Rev. Phys. Chem. 66, 241–262 (2015).

    CAS  Article  Google Scholar 

  5. 5.

    Kaiser, R. I., Parker, D. S. N. & Mebel, A. M. Reaction dynamics in astrochemistry: low-temperature pathways to polycyclic aromatic hydrocarbons in the interstellar medium. Annu. Rev. Phys. Chem. 66, 43–67 (2015).

    CAS  Article  Google Scholar 

  6. 6.

    Wang, T. et al. Dynamical resonances in chemical reactions. Chem. Soc. Rev. 47, 6744–6763 (2018).

    CAS  Article  Google Scholar 

  7. 7.

    Neufeld, D. A., Zmuidzinas, J., Schilke, P. & Phillips, T. G. Discovery of interstellar hydrogen fluoride. Astrophys. J. 488, L141–L144 (1997).

    CAS  Article  Google Scholar 

  8. 8.

    Agundez, M. et al. HIFI detection of hydrogen fluoride in the carbon star envelope IRC+10216. Astron. Astrophys. 533, L6 (2011).

    Article  Google Scholar 

  9. 9.

    Monje, R. R. et al. Herschel/HIFI observations of hydrogen fluoride toward Sagittarius B2(M). Astrophys. J. Lett. 734, L23 (2011).

    Article  Google Scholar 

  10. 10.

    Indriolo, N., Neufeld, D. A., Seifahrt, A. & Richter, M. J. Direct determination of the HF/H2 abundance ratio in interstellar gas. Astrophys. J. 764, 188 (2013).

    Article  Google Scholar 

  11. 11.

    Berteloite, C. et al. Kinetics and dynamics of the S(1D2) + H2 → SH + H reaction at very low temperatures and collision energies. Phys. Rev. Lett. 105, 203201 (2010).

    Article  Google Scholar 

  12. 12.

    Lara, M. et al. Dynamics of the S(1D2) + H2 reaction at collision energies approaching the cold regime: a stringent test for theory. Phys. Rev. Lett. 109, 133201 (2012).

    Article  Google Scholar 

  13. 13.

    Lara, M. et al. Observation of partial wave structures in the integral cross section of the S(1D2) + H2(j = 0) reaction. Phys. Chem. Chem. Phys. 13, 8127–8130 (2011).

    CAS  Article  Google Scholar 

  14. 14.

    Tizniti, M. et al. The rate of the F + H2 reaction at very low temperatures. Nat. Chem. 6, 141–145 (2014).

    CAS  Article  Google Scholar 

  15. 15.

    Schatz, G. C. Detecting resonance. Science 288, 1599–1600 (2000).

    CAS  Article  Google Scholar 

  16. 16.

    Fernandez-Alonso, F. & Zare, R. N. Scattering resonances in the simplest chemical reaction. Annu. Rev. Phys. Chem. 53, 67–99 (2002).

    CAS  Article  Google Scholar 

  17. 17.

    Liu, K. Crossed-beam studies of neutral reactions: state-specific differential cross sections. Annu. Rev. Phys. Chem. 52, 139–164 (2001).

    CAS  Article  Google Scholar 

  18. 18.

    Liu, K. Quantum dynamical resonances in chemical reactions: from A + BC to polyatomic systems. Adv. Chem. Phys. 149, 1–46 (2012).

    CAS  Article  Google Scholar 

  19. 19.

    Yang, X. M. & Zhang, D. H. Dynamics resonances in the fluorine atom reaction with the hydrogen molecule. Acc. Chem. Res. 41, 981–989 (2008).

    CAS  Article  Google Scholar 

  20. 20.

    Schatz, G. C., Bowman, J. M. & Kuppermann, A. Large quantum effects in the collinear F + H2 → HF + H reaction. J. Chem. Phys. 58, 4023–4025 (1973).

    CAS  Article  Google Scholar 

  21. 21.

    Wu, S.-F., Johnson, B. R. & Levine, R. D. Quantum mechanical computational studies of chemical reactions: III. Collinear A + BC reaction with some model potential energy surfaces. Mol. Phys. 25, 839–856 (1973).

    CAS  Article  Google Scholar 

  22. 22.

    Neumark, D. M. et al. Molecular beam studies of the F + D2 and F + HD reactions. J. Chem. Phys. 82, 3067–3077 (1985).

    CAS  Article  Google Scholar 

  23. 23.

    Neumark, D. M., Wodtke, A. M., Robinson, G. N., Hayden, C. C. & Lee, Y. T. Molecular beam studies of the F + H2 reaction. J. Chem. Phys. 82, 3045–3066 (1985).

    CAS  Article  Google Scholar 

  24. 24.

    Aoiz, F. J. et al. Classical dynamics for the F + H2 → HF + H reaction on a new ab initio potential energy surface: a direct comparison with experiment. Chem. Phys. Lett. 223, 215–226 (1994).

    CAS  Article  Google Scholar 

  25. 25.

    Castillo, J. F., Manolopoulos, D. E., Stark, K. & Werner, H. J. Quantum mechanical angular distributions for the F + H2 reaction. J. Chem. Phys. 104, 6531–6546 (1996).

    CAS  Article  Google Scholar 

  26. 26.

    Stark, K. & Werner, H. J. An accurate multireference configuration interaction calculation of the potential energy surface for the F + H2 → HF + H reaction. J. Chem. Phys. 104, 6515–6530 (1996).

    CAS  Article  Google Scholar 

  27. 27.

    Ren, Z. et al. Probing the resonance potential in the F atom reaction with hydrogen deuteride with spectroscopic accuracy. Proc. Natl Acad. Sci. USA 105, 12662–12666 (2008).

    CAS  Article  Google Scholar 

  28. 28.

    Skodje, R. T. et al. Resonance mediated chemical reaction: F + HD → HF + D. Phys. Rev. Lett. 85, 1206 (2000).

    CAS  Article  Google Scholar 

  29. 29.

    Dong, W. R. et al. Transition state spectroscopy of partial wave resonances in the F + HD reaction. Science 327, 1501–1502 (2010).

    CAS  Article  Google Scholar 

  30. 30.

    Manolopoulos, D. E. et al. The transition state of the F + H2 reaction. Science 262, 1852–1855 (1993).

    CAS  Article  Google Scholar 

  31. 31.

    Kim, J. B. et al. Spectroscopic observation of resonances in the F + H2 reaction. Science 349, 510–513 (2015).

    CAS  Article  Google Scholar 

  32. 32.

    Qiu, M. H. et al. Observation of Feshbach resonances in the F + H2 → HF + H reaction. Science 311, 1440 (2006).

    CAS  Article  Google Scholar 

  33. 33.

    Wang, X. A. et al. HF(v′ = 3) forward scattering in the F + H2 reaction: shape resonance and slow-down mechanism. Proc. Natl Acad. Sci. USA 105, 6227–6231 (2008).

    CAS  Article  Google Scholar 

  34. 34.

    Qiu, M. H. et al. High resolution time-of-flight spectrometer for crossed molecular beam study of elementary chemical reactions. Rev. Sci. Instrum. 76, 083107 (2005).

    Article  Google Scholar 

  35. 35.

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

    CAS  Article  Google Scholar 

  36. 36.

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

    CAS  Article  Google Scholar 

  37. 37.

    Neumark, D. M. Probing the transition state with negative ion photodetachment: experiment and theory. Phys. Chem. Chem. Phys. 7, 433–442 (2005).

    CAS  Article  Google Scholar 

  38. 38.

    Yu, D., Chen, J., Cong, S. L. & Sun, Z. Theoretical study of FH2 electron photodetachment spectra on new ab initio potential energy surfaces. J. Phys. Chem. A 119, 12193–12208 (2015).

    CAS  Article  Google Scholar 

  39. 39.

    Blondel, C., Delsart, C. & Goldfarb, F. Electron spectrometry at the μeV level and the electron affinities of Si and F. J. Phys. At. Mol. Opt. Phys. 34, L281–L288 (2001).

    CAS  Article  Google Scholar 

  40. 40.

    Chen, J., Sun, Z. & Zhang, D. H. An accurate potential energy surface for the F + H2 → HF + H reaction by the coupled-cluster method. J. Chem. Phys. 142, 024303 (2015).

    Article  Google Scholar 

  41. 41.

    Skouteris, D., Castillo, J. F. & Manolopoulos, D. E. ABC: a quantum reactive scattering program. Comput. Phys. Commun. 133, 128–135 (2000).

    CAS  Article  Google Scholar 

  42. 42.

    Sun, Z., Zhang, D. H. & Alexander, M. H. Time-dependent wavepacket investigation of state-to-state reactive scattering of Cl with para-H2 including the open-shell character of the Cl atom. J. Chem. Phys. 132, 034308 (2000).

    Article  Google Scholar 

  43. 43.

    Sun, Z., Yang, W. T. & Zhang, D. H. Higher-order split operator schemes for solving the Schrödinger equation in the time-dependent wave packet method: applications to triatomic reactive scattering calculations. Phys. Chem. Chem. Phys. 14, 1827–1845 (2012).

    CAS  Article  Google Scholar 

  44. 44.

    Lique, F., Li, G. L., Werner, H.-J. & Alexander, M. H. Non-adiabatic coupling and resonances in the F + H2 reaction at low energies. J. Chem. Phys. 134, 231101 (2011).

    Article  Google Scholar 

  45. 45.

    Alexander, M. H., Manolopoulos, D. & Werner, H.-J. An investigation of the F + H2 reaction based on a full ab initio description of the open-shell character of the F(2P) atom. J. Chem. Phys. 113, 11084 (2000).

    CAS  Article  Google Scholar 

  46. 46.

    Weichman, M. L. et al. Feshbach resonances in the exit channel of the F + CH3OH → HF + CH3O reaction observed using transition-state spectroscopy. Nat. Chem. 9, 950–955 (2017).

    CAS  Article  Google Scholar 

  47. 47.

    Sternberg, A. & Neufeld, D. The ratio of ortho- to para-H2 in photodissociation regions. Astrophys. J. 516, 371–380 (1999).

    CAS  Article  Google Scholar 

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Acknowledgements

C.X., Z.S., D.H.Z. and X.Y. acknowledge financial support for this research from the National Science Foundation of China (grants 21688102, 21590800, 21127902 and 21433009) and the Chinese Academy of Sciences (grants XDB 17010000). D.M.N. thanks the Air Force Office of Scientific Research for funding this research under grant no. FA9550-16-1-0097. M.H.A. thanks the US National Science Foundation for support under grant no. CHE-1565872.

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X.Y., D.H.Z., Z.S., C.X., D.M.N. and M.H.A. conceived and supervised the research. The experiments were carried out by T.Y., L.H., T.W., D.D. and C.X. Data analysis and interpretation were performed by T.Y., L.H., T.W., D.D., C.X. and X.Y. Theoretical calculations were performed by Z.S., J.C., F.L., M.H.A. and D.H.Z. The manuscript was written by X.Y., Z.S., M.H.A., D.Z. and D.M.N., with contributions from all authors. All authors contributed to discussions about the content of the paper.

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Correspondence to Millard H. Alexander or Zhigang Sun or Xueming Yang or Daniel M. Neumark.

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Supplementary Figs. 1–9, Supplementary Tables 1 and 2, Supplementary methods

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Yang, T., Huang, L., Xiao, C. et al. Enhanced reactivity of fluorine with para-hydrogen in cold interstellar clouds by resonance-induced quantum tunnelling. Nat. Chem. 11, 744–749 (2019). https://doi.org/10.1038/s41557-019-0280-3

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