Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Attosecond coupled electron and nuclear dynamics in dissociative ionization of H2

Nature Physics volume 14, pages 733–738 (2018)Cite this article

Subjects

Abstract

The interaction of an extreme-ultraviolet attosecond pulse with a molecular system suddenly removes electrons, which can lead to significant changes in the chemical bonding and hence to rearrangements of the residual molecular cation. The timescales of the electronic and nuclear dynamics are usually very different, thus supporting separate treatment. However, when light nuclei are involved, as in most organic and biological molecules containing atomic hydrogen, the correlation between electronic and nuclear motion cannot be ignored. Using an advanced attosecond pump–probe spectroscopic method, we show that the coupling between electronic and nuclear motion in H2 leaves a clear trace in the phase of the entangled electron–nuclear wave packet. This requires us to re-evaluate the physical meaning of the measured phase, which depends on the energy distribution between electrons and nuclei. The conclusions are supported by ab initio calculations that explicitly account for the coupling between electronic and nuclear dynamics.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: H2 dissociative photoionization.
Fig. 2: Cross-section and kinetic energy correlation diagrams.
Fig. 3: 3D nuclear–electron phase–time map.
Fig. 4: Relative molecular phases as a function of the photon energy.

Similar content being viewed by others

References

  1. Hentschel, M. et al. Attosecond metrology. Nature 414, 509–513 (2001).

    ADS  Google Scholar 

  2. Sansone, G. et al. Isolated single-cycle attosecond pulses. Science 314, 443–446 (2006).

    ADS  Google Scholar 

  3. Eckle, P. et al. Attosecond ionization and tunneling delay time measurements in helium. Science 322, 1525–1529 (2008).

    ADS  Google Scholar 

  4. Schultze, M. et al. Delay in photoemission. Science 328, 1658–1662 (2010).

    ADS  Google Scholar 

  5. Klünder, K. et al. Probing single-photon ionization on the attosecond time scale. Phys. Rev. Lett. 106, 143002 (2011).

    ADS  Google Scholar 

  6. Månsson, E. P. et al. Double ionization probed on the attosecond timescale. Nat. Phys. 10, 207–211 (2014).

    Google Scholar 

  7. Guenot, D. et al. Measurements of relative photoemission time delays in noble gas atoms. J. Phys. B 47, 245602 (2014).

    ADS  Google Scholar 

  8. Palatchi, C. et al. Atomic delay in helium, neon, argon and krypton. J. Phys. B 47, 245003 (2014).

    ADS  Google Scholar 

  9. Kotur, M. et al. Spectral phase measurement of a Fano resonance using tunable attosecond pulses. Nat. Commun. 7, 10566 (2016).

    ADS  Google Scholar 

  10. Jordan, I. et al. Spin-orbit delays in photoemission. Phys. Rev. A 95, 013404 (2017).

    ADS  Google Scholar 

  11. Sabbar, M. et al. Resonance effects in photoemission time delays. Phys. Rev. Lett. 115, 133001 (2015).

    ADS  Google Scholar 

  12. Cattaneo, L. et al. Comparison of attosecond streaking and RABBITT. Opt. Express 24, 29060–29076 (2016).

    ADS  Google Scholar 

  13. Haessler, S. et al. Phase-resolved attosecond near-threshold photoionization of molecular nitrogen. Phys. Rev. A 80, 011404 (2009).

    ADS  Google Scholar 

  14. Sansone, G. et al. Electron localization following attosecond molecular photoionization. Nature 465, 763–766 (2010).

    ADS  Google Scholar 

  15. Calegari, F. et al. Ultrafast electron dynamics in phenylalanine initiated by attosecond pulses. Science 346, 336–339 (2014).

    ADS  Google Scholar 

  16. Huppert, M., Jordan, I., Baykusheva, D., von Conta, A. & Wörner, H. J. Attosecond delays in molecular photoionization. Phys. Rev. Lett. 117, 093001 (2016).

    ADS  Google Scholar 

  17. Remacle, F. & Levine, R. D. An electronic time scale in chemistry. Proc. Natl Acad. Sci. USA 103, 6793–6798 (2006).

    ADS  Google Scholar 

  18. Vibok, A. & Balint-Kurti, G. G. Parametrization of complex absorbing potentials for time-dependent quantum dynamics. J. Phys. Chem. 96, 8712–8719 (1992).

    Google Scholar 

  19. Cavalieri, A. L. et al. Attosecond spectroscopy in condensed matter. Nature 449, 1029–1032 (2007).

    ADS  Google Scholar 

  20. Locher, R. et al. Energy-dependent photoemission delays from noble metal surfaces by attosecond interferometry. Optica 2, 405–410 (2015).

    ADS  Google Scholar 

  21. Bandrauk, A. D., Chelkowski, S. & Nguyen, H. S. Attosecond localization of electrons in molecules. Int. J. Quant. Chem. 100, 834–844 (2004).

    Google Scholar 

  22. Calvert, C. R., Bryan, W. A., Newell, W. R. & Williams, I. D. Time-resolved studies of ultrafast wavepacket dynamics in hydrogen molecules. Phys. Rep. 491, 1–28 (2010).

    ADS  Google Scholar 

  23. Ranitovic, P. et al. Attosecond vacuum UV coherent control of molecular dynamics. Proc. Natl Acad. Sci. USA 11, 912–917 (2014).

    ADS  Google Scholar 

  24. Lara-Astiaso, M. et al. Decoherence, control and attosecond probing of XUV-induced charge migration in biomolecules. A theoretical outlook. Faraday Discuss. 194, 41–59 (2016).

    ADS  Google Scholar 

  25. Vacher, M., Bearpark, M. J., Robb, M. A. & Malhado, J. P. Electron dynamics upon ionization of polyatomic molecules: coupling to quantum nuclear motion and decoherence. Phys. Rev. Lett. 118, 083001 (2017).

    ADS  Google Scholar 

  26. Muller, H. G. Reconstruction of attosecond harmonic beating by interference of two-photon transitions. Appl. Phys. B 74, S17–S21 (2002).

    ADS  Google Scholar 

  27. Paul, P. et al. Observation of a train of attosecond pulses from high harmonic generation. Science 292, 1689–1692 (2001).

    ADS  Google Scholar 

  28. Ullrich, J. et al. Recoil-ion and electron momentum spectroscopy: reaction-microscopes. Rep. Prog. Phys. 66, 1463–1545 (2003).

    ADS  Google Scholar 

  29. Dörner, R. et al. Cold target recoil ion momentum spectroscopy: a ‘momentum microscope’ to view atomic collision dynamics. Phys. Rep. 330, 95–192 (2000).

    ADS  Google Scholar 

  30. Sabbar, M. et al. Combining attosecond XUV pulses with coincidence spectroscopy. Rev. Sci. Instrum. 85, 103113 (2014).

    ADS  Google Scholar 

  31. Wickenhauser, M., Burgdörfer, J., Krausz, F. & Drescher, M. Time resolved Fano resonances. Phys. Rev. Lett. 94, 023002 (2005).

    ADS  MATH  Google Scholar 

  32. Sanz-Vicario, J. L., Bachau, H. & Martin, F. Time-dependent theoretical description of molecular autoionization produced by femtosecond XUV laser pulses. Phys. Rev. A 73, 033410 (2006).

    ADS  Google Scholar 

  33. Kling, M. F. et al. Control of electron localization in molecular dissociation. Science 312, 246–248 (2006).

    ADS  Google Scholar 

  34. Palacios, A., Sanz-Vicario, J. L. & Martín, F. Theoretical methods for attosecond electron and nuclear dynamics: applications to the H2 molecule. J. Phys. B 48, 242001 (2015).

    ADS  Google Scholar 

  35. Lafosse, A. et al. Molecular frame photoelectron angular distributions in dissociative photoionization of H2 in the region of the Q1 and Q2 doubly excited states. J. Phys. B 36, 4683–4702 (2003).

    ADS  Google Scholar 

  36. Martín, F. et al. Single photon-induced symmetry breaking of H2 dissociation. Science 315, 629–633 (2007).

    ADS  Google Scholar 

  37. Sánchez, I. & Martín, F. Resonant dissociative photoionization of H2 and D2. Phys. Rev. A 57, 1006–1017 (1998).

    ADS  Google Scholar 

  38. Ito, K., Hall, R. I. & Ukai, M. Dissociative photoionization of H2 and D2 in the energy region of 25–45 eV. J. Chem. Phys. 104, 8449–8457 (1996).

    ADS  Google Scholar 

  39. Palacios, A., Feist, J., González‐Castrillo, A., Sanz‐Vicario, J. L. & Martín, F. Autoionization of molecular hydrogen: where do the Fano lineshapes go? Chem. Phys. Chem. 14, 1456–1463 (2013).

    Google Scholar 

  40. Bucksbaum, P. H., Zavriyev, A., Muller, H. G. & Schumacher, D. W. Softening of the H2 + molecular bond in intense laser fields. Phys. Rev. Lett. 64, 1883–1886 (1990).

    ADS  Google Scholar 

  41. Zavriyev, A., Bucksbaum, P. H., Muller, H. G. & Schumacher, D. W. Ionization and dissociation of H2 in intense laser fields at 1.064 μm, 532 nm, and 355 nm. Phys. Rev. A 42, 5500–5513 (1990).

    ADS  Google Scholar 

  42. Giusti-Suzor, A., Mies, F. H., DiMauro, L. F., Charron, E. & Yang, B. Dynamics of H2 + in intense laser fields. J. Phys. B 28, 309–339 (1995).

    ADS  Google Scholar 

  43. Wigner, E. P. Lower limit for the energy derivative of the scattering phase shift. Phys. Rev. 98, 145–147 (1955).

    ADS  MathSciNet  MATH  Google Scholar 

  44. Argenti, L. et al. Control of photoemission delay in resonant two-photon transitions. Phys. Rev. A 95, 043426 (2017).

    ADS  Google Scholar 

  45. Sánchez, I. & Martín, F. The doubly excited states of the H2 molecule. J. Chem. Phys. 106, 7720–7730 (1997).

    ADS  Google Scholar 

  46. Latimer, C. J., Irvine, A. D., McDonald, M. A. & Savage, O. G. The dissociative photoionization of hydrogen via two-electron excitation at 27.5 eV and 30.5 eV. J. Phys. B 25, L211–L214 (1992).

    ADS  Google Scholar 

  47. Sánchez, I. & Martín, F. Dissociative photoionization of H2 and D2 by (30–37)-eV photons via 1Πu states. Phys. Rev. A 60, 2200–2206 (1999).

    ADS  Google Scholar 

  48. Aoto, T. et al. Dissociative photoionization of H2 at high photon energies: uncovering new series of doubly excited states. Chem. Phys. Lett. 389, 145–149 (2004).

    ADS  Google Scholar 

Download references

Acknowledgements

This work is supported by the European Research Council (ERC) advanced grants ERC-2012-ADG_20120216 and ERC with grant agreement 290853 XCHEM within the Seventh Framework Programme of the European Union. We also acknowledge the financial support from the Ministry of Economy and External Trade (MINECO) projects FIS2013-42002-R and FIS2016-77889-R, and the European COST Action XLIC CM1204, and the computer time from the Centro de Computación Científica-Universidad Autónoma de Madrid (CCC-UAM) and Marenostrum Supercomputer. A.P. acknowledges a Ramón y Cajal contract from the Ministerio de Economiía y Competitividad (Spain). F.M. acknowledges support from the ‘Severo Ochoa’ Programme for Centres of Excellence in R&D (MINECO, Grant SEV-2016-0686) and the ‘María de Maeztu’ Programme for Units of Excellence in R&D (MDM-2014-0377).

Author information

Author notes

  1. M. Lucchini

    Present address: Department of Physics, Politecnico di Milano, Milano, Italy

Authors and Affiliations

  1. Physics Department, ETH Zurich, Zurich, Switzerland

    L. Cattaneo, J. Vos, S. Heuser, L. Pedrelli, M. Lucchini, C. Cirelli & U. Keller

  2. Departamento de Química, Módulo 13, Universidad Autónoma de Madrid, Madrid, Spain

    R. Y. Bello, A. Palacios & F. Martín

  3. Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Madrid, Spain

    A. Palacios

  4. Empa – Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, Switzerland

    C. Cirelli

  5. Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nanociencia), Madrid, Spain

    F. Martín

  6. Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, Madrid, Spain

    F. Martín

Authors
  1. L. Cattaneo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. J. Vos
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. R. Y. Bello
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. Palacios
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. S. Heuser
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. L. Pedrelli
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. M. Lucchini
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. C. Cirelli
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. F. Martín
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. U. Keller
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

L.C., J.V., L.P. and S.H. performed the experimental measurements. L.C. and J.V. performed the experimental data analysis. R.Y.B., A.P. and F.M. performed the theoretical calculations and analysis. L.C., J.V., M.L., C.C., R.B., A.P., F.M. and U.K. contributed to the data interpretation, scientific discussion and to the manuscript.

Corresponding author

Correspondence to L. Cattaneo.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplemenatry Chapters 1–6, Supplementary Figures 1–8

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Cattaneo, L., Vos, J., Bello, R.Y. et al. Attosecond coupled electron and nuclear dynamics in dissociative ionization of H2. Nature Phys 14, 733–738 (2018). https://doi.org/10.1038/s41567-018-0103-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41567-018-0103-2

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing