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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Cohen, H. D. & Fano, U. Interference in the photo-ionization of molecules. Phys. Rev. 150, 30–33 (1966)
Lein, M. et al. Role of the intermolecular phase in high harmonic generation. Phys. Rev. Lett. 88, 183903 (2002)
Itatani, J. et al. Tomographic imaging of molecular orbitals. Nature 432, 867–871 (2004)
Kanai, T., Minemoto, S. & Sakai, H. Quantum interference during high-order harmonic generation from aligned molecules. Nature 435, 470–474 (2005)
Vozzi, C. et al. Controlling two-center interference in molecular high harmonic generation. Phys. Rev. Lett. 95, 153902 (2005)
Baker, S. et al. Probing proton dynamics in molecules on an attosecond time scale. Science 312, 424–427 (2006)
Baker, S. et al. Dynamic two-center interference in high-order harmonic generation from molecules with attosecond nuclear motion. Phys. Rev. Lett. 101, 053901 (2008)
Boutu, W. et al. Coherent control of attosecond emission from aligned molecules. Nature Phys. 4, 545–549 (2008)
Zhou, X. et al. Molecular recollision interferometry in high harmonic generation. Phys. Rev. Lett. 100, 073902 (2008)
Li, W. et al. Time-resolved dynamics in N2O4 probed using high harmonic generation. Science 322, 1207–1211 (2006)
McFarland, B. K. et al. High harmonic generation from multiple orbitals in N2 . Science 322, 1232–1235 (2006)
Rosca-Pruna, F. & Vrakking, M. J. J. Experimental observation of revival structures in picosecond laser-induced alignment of I2 . Phys. Rev. Lett. 87, 153902 (2001)
Stapelfeldt, H. & Seideman, T. Aligning molecules with strong laser pulses. Rev. Mod. Phys. 75, 543–557 (2003)
Le, A. T., Morishita, T. & Lin, C. D. Extraction of the species-dependent dipole amplitude and phase from high-order harmonic spectra in rare-gas atoms. Phys. Rev. A 78, 023814 (2008)
Morishita, T., Le, A. T., Chen, Z. & Lin, C. D. Accurate retrieval of structural information from laser-induced photoelectron and high-order harmonic spectra by few-cycle laser pulses. Phys. Rev. Lett. 100, 013903 (2008)
Le, V. H., Le, A. T., Xie, R. H. & Lin, C. D. Theoretical analysis of dynamic chemical imaging with lasers using high-order harmonic generation. Phys. Rev. A 76, 013414 (2007)
Le, A. T., Tong, X. M. & Lin, C. D. Evidence of two-center interference in high-order harmonic generation from CO2 . Phys. Rev. A 73, 041402 (2006)
Lein, M. Molecular imaging using recolliding electrons. J. Phys. B 40, R135–R173 (2007)
Tong, X. M., Zhao, Z. X. & Lin, C. D. Theory of molecular tunneling ionization. Phys. Rev. Lett. 66, 033402 (2002)
Muth-Böhm, J., Becker, A. & Faisal, F. H. M. Suppressed molecular ionization for a class of diatomics in intense femtosecond laser fields. Phys. Rev. Lett. 85, 2280–2283 (2000)
Zerne, R. et al. Phase locked high-order harmonic emission. Phys. Rev. Lett. 79, 1006–1009 (1997)
Corkum, P. B. Plasma perspective on strong field multiphoton ionization. Phys. Rev. Lett. 71, 1994–1997 (1993)
Mairesse, Y. et al. Attosecond synchronization of high-harmonic soft X-rays. Science 302, 1540–1543 (2003)
Lein, M. Attosecond probing of vibrational dynamics with high-harmonic generation. Phys. Rev. Lett. 94, 053004 (2005)
Ortiz, J. V. Quasiparticle approximations and electron propagator theory. Int. J. Quantum Chem. 95, 593–599 (2003)
Pavicic, D. et al. Direct measurement of the angular dependence of ionization for N2, O2, and CO2 in intense laser fields. Phys. Rev. Lett. 98, 243001 (2007)
Lewenstein, M. et al. Theory of high harmonic generation by low-frequency laser fields. Phys. Rev. A 49, 2117–2132 (1994)
Descamps, D. et al. Extreme ultraviolet interferometry measurements with high order harmonics. Opt. Lett. 25, 135–137 (2000)
Corsi, C., Pirri, A., Sali, E., Tortora, A. & Bellini, M. Direct interferometric measurement of the atomic dipole phase in high-order harmonic generation. Phys. Rev. Lett. 97, 023901 (2006)
Dudovich, N. et al. Measuring and controlling the birth of attosecond XUV pulses. Nature Phys. 2, 781–786 (2006)
Lezius, M. et al. Nonadiabatic multielectron dynamics in strong field molecular ionization. Phys. Rev. Lett. 86, 51–89 (2001)
Markevitch, A. N. et al. Nonadiabatic dynamics of polyatomic molecules and ions in strong laser fields. Phys. Rev. A 68, 011402 (2003)
Litvinyuk, I. et al. Shakeup excitation during optical tunnel ionization. Phys. Rev. Lett. 94, 033003 (2005)
Wagner, N. et al. Monitoring molecular dynamics using coherent electrons from high-harmonic generation. Proc. Natl Acad. Sci. USA 103, 13279–13285 (2006)
Remetter, T. et al. Attosecond electron wave packet interferometry. Nature Phys. 2, 323–326 (2006)
Corkum, P. B. & Krausz, F. Attosecond science. Nature Phys. 3, 381–387 (2007)
Levesque, J. et al. Polarization state of high-order harmonic emission from aligned molecules. Phys. Rev. Lett. 99, 243001 (2007)
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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Smirnova, O., Mairesse, Y., Patchkovskii, S. et al. High harmonic interferometry of multi-electron dynamics in molecules. Nature 460, 972–977 (2009). https://doi.org/10.1038/nature08253
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