Femtosecond-resolved observation of the fragmentation of buckminsterfullerene following X-ray multiphoton ionization

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Abstract

X-ray free-electron lasers have, over the past decade, opened up the possibility of understanding the ultrafast response of matter to intense X-ray pulses. In earlier research on atoms and small molecules, new aspects of this response were uncovered, such as rapid sequences of inner-shell photoionization and Auger ionization. Here, we studied a larger molecule, buckminsterfullerene (C60), exposed to 640 eV X-rays, and examined the role of chemical effects, such as chemical bonds and charge transfer, on the fragmentation following multiple ionization of the molecule. To provide time resolution, we performed femtosecond-resolved X-ray pump/X-ray probe measurements, which were accompanied by advanced simulations. The simulations and experiment reveal that despite substantial ionization induced by the ultrashort (20 fs) X-ray pump pulse, the fragmentation of C60 is considerably delayed. This work uncovers the persistence of the molecular structure of C60, which hinders fragmentation over a timescale of hundreds of femtoseconds. Furthermore, we demonstrate that a substantial fraction of the ejected fragments are neutral carbon atoms. These findings provide insights into X-ray free-electron laser-induced radiation damage in large molecules, including biomolecules.

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Fig. 1: Comparison between the experimental and theoretical data for the atomic carbon ion yields as a function of the time delay between the X-ray pump and the X-ray probe.
Fig. 2: Identification of the parent fragments responsible for the observed C ion charge states.
Fig. 3: KE evolution of the ion charge states as a function of the pump–probe delay.
Fig. 4: Real-space and real-time simulation dynamics of C6013+ induced by a single XFEL pulse centred at t = 0 fs.

Data availability

The data that support the findings of this study are available from the corresponding author on reasonable request.

Code availability

The released version of the software underlying the findings of this study is available from Z.J. and R.S (at xraypac@mail.desy.de). and more information is available at http://www.desy.de/~xraypac.

Change history

  • 10 October 2019

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

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Acknowledgements

This work was funded by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy, grant nos. DE-SC0012376 (N.B., R.O. and H.X.) and DE-FG02-86ER13491 (D.R.). Use of the Linac Coherent Light Source (LCLS), SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. We thank the Knut and Alice Wallenberg Foundation and the Swedish Research Council for support. This work was supported in part by the Hamburg Centre for Ultrafast Imaging centre of excellence of the Deutsche Forschungsgemeinschaft, EXC 1074, project ID 194651731 (Z.J., K.T., S.-K.S. and R.S.). A.S.-G. was funded by the Science and Technolgy Facilities Council (STFC). K.M., H.F. and K.U. acknowledge support by XFEL priority strategy program of MEXT. K.U. and H.F. acknowledge support by the Five-Star Alliance of the Network Joint Research Center of Materials and Devices, and by the TAGEN project. We thank A. LaForge for helpful discussions.

Author information

A.S.-G. and Z.J. contributed equally to this work. N.B. conceived and coordinated the project. N.B., Z.J. and R.S. wrote the paper with contributions from all the authors. R.O. and H.X. developed and tested the C60 source before the experiment, and R.O., H.X. and T.J.A.W. maintained the source during the experiment. R.J.S. and R.F. designed the spectrometer. A.L. prepared the two pulses for the X-ray pump–probe scheme. T.O., R.O., R.J.S., H.X. and R.F. prepared the experiment. T.O., J.C., A.S.-G., H.X., R.O., R.J.S., A.L., L.F., T.B., J.D.B., T.J.A.W., D.R., R.C., K.S., S.A., N.N., R.F., K.U., K.M., J.P.M., C.P.S., T.P., H.F. and N.B. carried out the experiment. Z.J., S.-K.S., K.T. and R.S. performed the theoretical work. A.S.-G., R.O., T.B., T.J.A.W. and L.J.F. contributed to the experimental data analysis.

Correspondence to N. Berrah.

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