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Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

Nature Physics volume 7, pages 612–615 (2011)Cite this article

Abstract

Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems1,2,3,4,5,6. By contrast, time-resolved structural-dynamics methods such as electron7,8,9,10 or X-ray diffraction11 and X-ray absorption12 yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy13,14,15 and high-harmonic generation16,17: in both cases, this sensitivity derives from the ionization-matrix element18,19. Here we demonstrate a time-resolved molecular-frame photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during the non-adiabatic photodissociation of carbon disulphide demonstrate how the purely electronic rearrangements of the valence electrons can be projected from inherently coupled electronic–vibrational dynamics. Combined with ongoing efforts in molecular frame alignment20 and orientation21,22, TRMFPADs offer the promise of directly imaging valence-electron dynamics during molecular processes without involving the use of strong, highly perturbing laser fields23.

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Figure 1: Conceptual picture of TRMFPADs as a probe of valence-electronic dynamics during CS2 photodissociation.
Figure 2: Experimental TRPES and TRMFPADs from CS2 photodissociation.
Figure 3: Calculated TRMFPADs from a wavepacket in CS2(C), showing good agreement with the experimental results of Fig. 2.

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Acknowledgements

We thank Guorong Wu (NRC Canada) for assistance with the alignment experiments, and Vincent McKoy (Caltech) for helpful discussion.

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Authors and Affiliations

  1. Steacie Institute for Molecular Sciences, National Research Council, 100 Sussex Drive, Ottawa, Ontario K1A 0R6, Canada

    Paul Hockett, Christer Z. Bisgaard & Albert Stolow

  2. Department of Chemistry, University of Copenhagen, Copenhagen DK-2100, Denmark

    Christer Z. Bisgaard

  3. Department of Chemistry, Queen’s University, Kingston, Ontario K7L 3N6, Canada

    Owen J. Clarkin & Albert Stolow

Authors
  1. Paul Hockett
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  2. Christer Z. Bisgaard
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  3. Owen J. Clarkin
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  4. Albert Stolow
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Contributions

C.Z.B. and A.S. planned the experiments. C.Z.B. and O.J.C. recorded experimental data. P.H. developed theoretical models and calculated TRMFPADs. O.J.C. calculated ab initio potential-energy surfaces. C.Z.B. and P.H. analysed data. All authors discussed the data and modelling, and contributed to the manuscript.

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Correspondence to Albert Stolow.

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The authors declare no competing financial interests.

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Hockett, P., Bisgaard, C., Clarkin, O. et al. Time-resolved imaging of purely valence-electron dynamics during a chemical reaction. Nature Phys 7, 612–615 (2011). https://doi.org/10.1038/nphys1980

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