Multi-channel electronic and vibrational dynamics in polyatomic resonant high-order harmonic generation

High-order harmonic generation in polyatomic molecules generally involves multiple channels of ionization. Their relative contribution can be strongly influenced by the presence of resonances, whose assignment remains a major challenge for high-harmonic spectroscopy. Here we present a multi-modal approach for the investigation of unaligned polyatomic molecules, using SF6 as an example. We combine methods from extreme-ultraviolet spectroscopy, above-threshold ionization and attosecond metrology. Fragment-resolved above-threshold ionization measurements reveal that strong-field ionization opens at least three channels. A shape resonance in one of them is found to dominate the signal in the 20-26 eV range. This resonance induces a phase jump in the harmonic emission, a switch in the polarization state and different dynamical responses to molecular vibrations. This study demonstrates a method for extending high-harmonic spectroscopy to polyatomic molecules, where complex attosecond dynamics are expected

Time-resolved predissociation of the vibrationless level of the B state of CH3I

The predissociation dynamics of the vibrationless level of the first Rydberg state 6s (B 2E) state of CH3I has been studied by femtosecond-resolved velocity map imaging of both the CH3 and I photofragments. The kinetic energy distributions of the two fragments have been recorded as a function of the pump-probe delay, and as a function of excitation within the umbrella and stretching vibrational modes of the CH3 fragment. These observations are made by using (2+1) Resonant Enhanced MultiPhoton Ionization (REMPI) via the 3pz 2A2" state of CH3 to detect specific vibrational levels of CH3. The vibrational branching fractions of the CH3 are recovered by using the individual vibrationally state-selected CH3 distributions to fit the kinetic energy distribution obtained by using nonresonant multiphoton ionization of either the I or CH3 fragment. The angular distributions and rise times of the two fragments differ significantly. These observations can be rationalized through a consideration of the alignment of the CH3 fragment and the effect of this alignment on its detection efficiency. Two extra dissociation channels are detected: one associated with Rydberg states near 9.2 eV that were observed previously in photoelectron studies, and one associated with photodissociation of the parent cation around 15 eV.Comment: submitted Physical Chemistry Chemical Physics (2011

A table-top ultrashort light source in the extreme ultraviolet for circular dichroism experiments

Circular dichroism in the extreme ultraviolet range is broadly used as a sensitive structural probe of matter, from the molecular photoionization of chiral species1, 2, 3 to the magnetic properties of solids4. Extending such techniques to the dynamical regime has been a long-standing quest of solid-state physics and physical chemistry, and was only achieved very recently5 thanks to the development of femtosecond circular extreme ultraviolet sources. Only a few large facilities, such as femtosliced synchrotrons6, 7 or free-electron lasers8, are currently able to produce such pulses. Here, we propose a new compact and accessible alternative solution: resonant high-order harmonic generation of an elliptical laser pulse. We show that this process, based on a simple optical set-up, delivers bright, coherent, ultrashort, quasi-circular pulses in the extreme ultraviolet. We use this source to measure photoelectron circular dichroism on chiral molecules, opening the route to table-top time-resolved femtosecond and attosecond chiroptical experiments