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Tuesday, 19 June 2012

Amelle: Conical Intersection Dynamics in NO2 Probed by Homodyne High-Harmonic Spectroscopy

Conical Intersection Dynamics in NO2 Probed by Homodyne High-Harmonic Spectroscopy
  1. D. M. Villeneuve1
+Author Affiliations
  1. 1Joint Laboratory for Attosecond Science, National Research Council of Canada and University of Ottawa, 100 Sussex Drive, Ottawa, Ontario, Canada K1A 0R6.
  2. 2Laboratorium für Physikalische Chemie, Eidgenössische Technische Hochschule Zürich, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland.
  3. 3Centre Lasers Intenses et Applications, Université de Bordeaux, CEA, CNRS, UMR5107, 351 Cours de la Libération, 33405 Talence, France.
  4. 4Laboratoire Collisions Agrégats Réactivité (IRSAMC), UPS, Université de Toulouse, F-31062 Toulouse, France and CNRS, UMR 5589, F-31062 Toulouse, France
  1. *To whom correspondence should be addressed. E-mail:


Conical intersections play a crucial role in the chemistry of most polyatomic molecules, ranging from the simplest bimolecular reactions to the photostability of DNA. The real-time study of the associated electronic dynamics poses a major challenge to the latest techniques of ultrafast measurement. We show that high-harmonic spectroscopy reveals oscillations in the electronic character that occur in nitrogen dioxide when a photoexcited wave packet crosses a conical intersection. At longer delays, we observe the onset of statistical dissociation dynamics. The present results demonstrate that high-harmonic spectroscopy could become a powerful tool to highlight electronic dynamics occurring along nonadiabatic chemical reaction pathways.

Tuesday, 12 June 2012

Thomas Gaumnitz: Chirped Auger emission at FLASH reveals long-range electron correlation

The energy of Auger electrons, i.e. secondary electrons emitted after a non-radiative decay of a deeply bound electronic core-hole, is an intrinsic property of the electronic structure of the excited atom and does not directly rely on the energy of the exciting photon, electron or ion. The electron emission is not mono-energetic, though; the fast - attosecond to femtosecond - decay times imply corresponding spectral widths in a range of a few tens of meV to a few eV. This time-energy correspondence suggests a uniform distribution of all energy components over time. In this work, we demonstrate that under spectroscopically relevant conditions, this presumption is wrong. Instead, our time-resolved experiments show evidence of an energetic chirp, i.e. a pronounced time-dependent variation of the Auger-electrons´ kinetic energy. It appears as a consequence of the correlated motion of both photo- and Auger electrons in the Coulomb field of the remaining ion. While the underlying mechanism - also known as ‘post-collision interaction’ (PCI) - has extensively been discussed in the literature, no attention has so far been paid to the consequence of the effect for the temporal properties of the escaping electron wave packets. We visualize this temporal energy variation by superimposing 13.5nm XUV pulses from FLASH with the oscillating electric field of a strong terahertz (THz) wave from the FLASH THz undulator in a xenon gas-target. Significantly, modified widths of kinetic energy spectra for opposite field gradients clearly indicate a chirp (see Fig. 1).

Figure 1: Kinetic energy spectra of xenon Auger lines formed after absorption of XUV photons in the presence of a THz field. The modified widths of the Auger lines for opposite field gradients indicate an energy chirp.

The experiments have been confirmed in the laboratory where a high harmonics XUV source and a laser based THz source were employed. The observed spectral modulations are reproduced with semi-classical as well as  quantum simulations, and are explained by an analytical model, which includes PCI in the presence of a time-dependent streaking field.