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XUV multiphoton ionization of molecules is commonly used in free-electron laser experiments to study charge transfer dynamics. However, molecular dissociation and electron dynamics, such as multiple photon absorption, Auger decay, and charge transfer, often happen on competing time scales, and the contributions of individual processes can be difficult to unravel. We experimentally investigate the Coulomb explosion dynamics of methyl iodide upon core–hole ionization of the shallow inner-shell of iodine (4d) and classically simulate the fragmentation by phenomenologically introducing ionization dynamics and charge transfer. Under our experimental conditions with medium fluence and relatively long XUV pulses (∼75 fs), we find that fast Auger decay prior to charge transfer significantly contributes to the charging mechanism, leading to a yield enhancement of higher carbon charge states upon molecular dissociation. Furthermore, we argue for the existence of another charging mechanism for the weak fragmentation channels leading to triply charged carbon atoms. This study shows that classical simulations can be a useful tool to guide the quantum mechanical description of the femtosecond dynamics upon multiphoton absorption in molecular systems.

Rydberg excitations in the vacuum ultraviolet spectral range may open up molecular photoreaction pathways not accessible from lower-lying valence states. Here, single-shot UV/VUV pump–probe spectroscopy was used to study the photodissociation dynamics of iodomethane after 268 nm excitation in the A-band and excitation of the 6p (2E3/2) Rydberg state at 161 nm. By combining weak-field VUV single-photon ionization with sub-10 fs temporal resolution and the superior statistical accuracy of the single-shot technique, sub-30 fs wave packet dynamics upon excitation in the A-band by a UV pump pulse were disclosed. Population transfer from the Rydberg state to the 2 1A1 valence state leading to 100 fs dissociation dynamics was observed by utilizing the same methodology in a VUV-pump/UV-probe scheme.

International Conference on Spectral Lines Shapes, Dublin, Ireland, 17 Jun 2018 - 22 Jun 2018; Journal of physics / Conference Series Conference Series 1289, 012030 - (2019). doi:10.1088/1742-6596/1289/1/012030, In this work, we present measurements of the intensity-dependent photoelectron spectrum of Kr irradiated by the FLASH FEL tuned to a photon energy of 25.8 eV. Intensity dependent photoelectron spectra were obtained with the aid of a Velocity Map Imaging (VMI) spectrometer. As the FEL photon energy is close to threshold, two photon sequential double ionization is favoured. The number of open channels is kept to a minimum and leading to a simple description of the process., Published by IOP Publ., Bristol

International audience; Due to its element and site specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here, we show that time-resolved inner-shell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane (CH3I) is investigated by ionization above the iodine 4d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal-field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules.

The dynamics following laser-induced molecular photodissociation of gas-phase CH2BrI at 271.6 nm were investigated by time-resolved Coulomb-explosion imaging using intense near-IR femtosecond laser pulses. The observed delay-dependent photofragment momenta reveal that CH2BrI undergoes C-I cleavage, depositing 65.6% of the available energy into internal product states, and that absorption of a second UV photon breaks the C-Br bond of CH2Br. Simulations confirm that this mechanism is consistent with previous data recorded at 248 nm, demonstrating the sensitivity of Coulomb-explosion imaging as a real-time probe of chemical dynamics.

Physical review / A 96(1), 013428 (2017). doi:10.1103/PhysRevA.96.013428, We present a joint experimental and theoretical study of the VUV-induced dynamics of $H_2O$ and its deuterated isotopologues in the first excited state $(A^1B_1)$ utilizing a VUV-pump VUV-probe scheme combined with $ab$ initio classical trajectory calculations. 16-fs VUV pulses centered at 161 nm created by fifth-order harmonic generation are employed for single-shot pump-probe measurements. Combined with a precise determination of the VUV pulses' temporal profile, they provide the necessary temporal resolution to elucidate sub-10-fs dissociation dynamics in the 1+1 photon ionization time window. Ionization with a single VUV photon complements established strong-field ionization schemes by disclosing the molecular dynamics under perturbative conditions. Kinetic isotope effects derived from the pump-probe experiment are found to be in agreement with our by ab initio classical trajectory calculations, taking into account photoionization cross sections for the ground and first excited state of the water cation., Published by Inst., Woodbury, NY

Synopsis In the interstellar medium polycyclic aromatic hydrocarbon molecules (PAH) are exposed to strong ionizing radation leading to complex organic photochemistry. We investigated these ultrafast fragmentation reactions after ionization of the PAHs phenanthrene, fluorene and pyrene at a wavelength of 30.3 nm using pump probe spectroscopy at a free electron laser. We observe double ionization and afterwards hydrogen abstraction and acetylene loss with characteristic time scales for the reaction processes below one hundred femtoseconds.

Physical review / A covering atomic, molecular, and optical physics and quantum information 94(3), 033411(2016). doi:10.1103/PhysRevA.94.033411, Molecular wave-packet dynamics in oxygen are studied in the time domain, using a single-color VUVpump–VUV-probe scheme. 17-fs VUV pulses, centered at 161 nm are generated via high-order harmonicgeneration driven by an intense 800-nm pulse leading to VUV pulse energies that reach 1.1 μJ per pulse. Anall-reflective interferometric pump-probe scheme is used for studying the delay dependence of the molecularoxygen ion signal with simultaneous nonresonant photoionization of krypton as a precise timing-reference.Access to the excited dissociative state lifetime is provided by the resulting delay-dependent O$_{2}^{+}$ signal,ultimately limited by the molecular ionization window. The ability to use a two-photon VUV probe providesthe delay-dependent detection of O$^+$ as an additional observable, extending the dissociation observationwindow., Published by Inst., Woodbury, NY

We demonstrate the generation of microjoule level, sub-20-fs, Ti:Sa fifth-harmonic pulses utilizing a loose-focusing geometry in a long Ar gas cell. The VUV pulses centered at 161.8 nm reach pulse energies of 1.1 μJ per pulse, while the corresponding pulse duration is measured with a second-order, fringe-resolved autocorrelation scheme to be 18±1 fs. Nonresonant, two-photon ionization of Kr and three-photon ionization of Ne verify the fifth-harmonic pulse high-intensity content and indicate the feasibility of multi-photon VUV pump-VUV probe studies of ultrafast atomic and molecular dynamics.

Journal of optics 20(2), 024018 (2018). doi:10.1088/2040-8986/aaa326, The development of ultra-short intense laser sources in the visible and extreme ultraviolet (XUV) spectral range has led to fascinating studies in laser-matter interactions and attosecond science. In the majority of these studies, the system under investigation interacts with a focused light beam, which ionizes the system. The ionization products are usually measured by devices, which spatiotemporally integrate the ionization signal originating from the entire focal area, discarding in this way valuable information about the ionization dynamics that take place in the interaction volume. Here, we review a recently developed approach in measuring the spatially resolved photoionization yields resulting from the interaction of infrared (IR)/XUV ultra-short light pulses in gas phase media. We show how this approach enables (a) the in situ focus diagnostic, (b) quantitative studies of linear and non-linear ionization processes in the IR/XUV regime, (c) single-shot XUV-pump-XUV-probe studies and (d) single-shot 2nd-order XUV autocorrelation measurements., Published by IOP Publ., Bristol