For the past several decades, we have been able to directly probe the motion of atoms that is associated with chemical transformations and which occurs on the femtosecond (10−15-s) timescale. However, studying the inner workings of atoms and molecules on the electronic timescale1,2,3,4 has become possible only with the recent development of isolated attosecond (10−18-s) laser pulses5. Such pulses have been used to investigate atomic photoexcitation and photoionization6,7 and electron dynamics in solids8, and in molecules could help explore the prompt charge redistribution and localization that accompany photoexcitation processes. In recent work, the dissociative ionization of H2 and D2 was monitored on femtosecond timescales9 and controlled using few-cycle near-infrared laser pulses10. Here we report a molecular attosecond pump–probe experiment based on that work: H2 and D2 are dissociatively ionized by a sequence comprising an isolated attosecond ultraviolet pulse and an intense few-cycle infrared pulse, and a localization of the electronic charge distribution within the molecule is measured that depends—with attosecond time resolution—on the delay between the pump and probe pulses. The localization occurs by means of two mechanisms, where the infrared laser influences the photoionization or the dissociation of the molecular ion. In the first case, charge localization arises from quantum mechanical interference involving autoionizing states and the laser-altered wavefunction of the departing electron. In the second case, charge localization arises owing to laser-driven population transfer between different electronic states of the molecular ion. These results establish attosecond pump–probe strategies as a powerful tool for investigating the complex molecular dynamics that result from the coupling between electronic and nuclear motions beyond the usual Born–Oppenheimer approximation.

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This work is part of the research programs of the Stichting voor Fundamenteel Onderzoek der Materie, which is financially supported by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek, and of the Spanish Ministerio de Ciencia e Innovación, project no. FIS2007-60064. We acknowledge support from MC-RTN XTRA (FP6-505138), the MC-EST MAXLAS, Laserlab Europe (Integrated Infrastructure Initiative Contract RII3-CT-2003-506350, proposal cusbo001275), the European COST Action CUSPFEL (CM0702), the Mare Nostrum Barcelona Supercomputer Center, the Centro de Computación Científica UAM, the Netherlands National Computing Facilities foundation, Stichting Academisch Rekencentrum Amsterdam, Programme Alβan for Latin America (E07D401391CO), the Universidad de Antioquia, the COLCIENCIAS agency, the Swedish Research Council, the Deutsche Forschungsgemeinschaft via the Emmy Noether Programme and the Cluster of Excellence: Munich Centre for Advanced Photonics.

Author information

Author notes

    • G. Sansone
    • , F. Kelkensberg
    • , J. F. Pérez-Torres
    •  & F. Morales

    These authors contributed equally to this work.


  1. CNR-INFM, National Laboratory for Ultrafast and Ultraintense Optical Science, Department of Physics, Politecnico of Milan, Piazza L. da Vinci 32, 20133 Milano, Italy

    • G. Sansone
    • , E. Benedetti
    • , F. Ferrari
    •  & M. Nisoli
  2. FOM-Institute AMOLF, Science Park 104, 1098 XG Amsterdam, The Netherlands

    • F. Kelkensberg
    • , W. Siu
    • , O. Ghafur
    • , P. Johnsson
    •  & M. J. J. Vrakking
  3. Departamento de Química, C-9, Universidad Autónoma de Madrid, 28049 Madrid, Spain

    • J. F. Pérez-Torres
    • , F. Morales
    •  & F. Martín
  4. Max-Planck Institut für Quantenoptik, Hans-Kopfermann Strasse 1, D-85748 Garching, Germany

    • M. F. Kling
    • , S. Zherebtsov
    •  & I. Znakovskaya
  5. Department of Physics, Lund University, PO Box 118, SE-221 00 Lund, Sweden

    • P. Johnsson
    • , M. Swoboda
    •  & A. L’Huillier
  6. Université Lyon 1/CNRS/LASIM, UMR 5579, 43 Boulevard Du 11 Novembre 1918, F-69622 Villeurbane, France

    • F. Lépine
  7. Grupo de Física Atómica y Molecular, Instituto de Física, Universidad de Antioquia, AA1226 Medellín, Colombia

    • J. L. Sanz-Vicario
  8. Department of Physics, Imperial College London, South Kensington Campus, SW7 2AZ, London, UK

    • M. Yu. Ivanov
  9. Max-Born-Institut, Max-Born Strasse 2A, D-12489 Berlin, Germany

    • M. J. J. Vrakking


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G.S. was responsible for the construction of the attosecond pump–probe set-up and the experiments on H2 and D2. F.K. was responsible for the experiments on H2 and D2 and the development of the semi-classical model. M.Yu.I. helped with the semi-classical model. J.F.P.-T. and F. Morales were responsible for the construction of the close-coupling code and the calculations using this code. M.F.K., W.S., O.G., P.J., M.S., E.B., F.F., F.L., S.Z. and I.Z. contributed to the experiments, which were carried out in three prolonged experimental sessions over almost 18 months. M.N. was in charge of the laboratory where the experiments were performed. A.L’H. supervised M.S. and P.J. F. Martin supervised F. Morales and J.F.P.-T. and was in charge of work with the TDSE model. J.L.S.-V. helped with the TDSE model. M.J.J.V. supervised F.K., W.S., O.G. and P.J. and was responsible for the overall coordination of the project

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to M. J. J. Vrakking.

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