High harmonic interferometry of multi-electron dynamics in molecules

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High harmonic emission occurs when an electron, liberated from a molecule by an incident intense laser field, gains energy from the field and recombines with the parent molecular ion. The emission provides a snapshot of the structure and dynamics of the recombining system, encoded in the amplitudes, phases and polarization of the harmonic light. Here we show with CO2 molecules that high harmonic interferometry can retrieve this structural and dynamic information: by measuring the phases and amplitudes of the harmonic emission, we reveal ‘fingerprints’ of multiple molecular orbitals participating in the process and decode the underlying attosecond multi-electron dynamics, including the dynamics of electron rearrangement upon ionization. These findings establish high harmonic interferometry as an effective approach to resolving multi-electron dynamics with sub-Ångström spatial resolution arising from the de Broglie wavelength of the recombining electron, and attosecond temporal resolution arising from the timescale of the recombination event.

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Figure 1: Pictorial schemes of multichannel interference in high harmonic generation, for two channels.
Figure 2: Contributions of different molecular orbitals to the harmonic emission.
Figure 3: Harmonic phase interferometry.
Figure 4: Harmonic spectra in CO 2 molecules.
Figure 5: Reconstruction of the hole dynamics.


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We appreciate discussions with A. Stolow and M. Spanner. This research was partially supported by the NSERC SRO and an AFOSR grant. O.S. acknowledges the Leibniz SAW award, and M.I. acknowledges support from the Alexander von Humboldt foundation.

Author Contributions O.S., S.P. and M.Y.I. developed theory, and Y.M., N.D., D.V. and P.C. performed experiments. All authors contributed to the analysis of data and writing the paper.

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Correspondence to Olga Smirnova.

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Smirnova, O., Mairesse, Y., Patchkovskii, S. et al. High harmonic interferometry of multi-electron dynamics in molecules. Nature 460, 972–977 (2009) doi:10.1038/nature08253

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