Femtosecond XUV Pulses Research Articles

UV-induced dissociation of CH2BrI probed by intense femtosecond XUV pulses

The ultraviolet (UV)-induced dissociation and photofragmentation of gas-phase CH2BrI molecules induced by intense femtosecond extreme ultraviolet (XUV) pulses at three different photon energies are studied by multi-mass ion imaging. Using a UV-pump–XUV-probe scheme, charge transfer between highly charged iodine ions and neutral CH2Br radicals produced by C–I bond cleavage is investigated. In earlier charge-transfer studies, the center of mass of the molecules was located along the axis of the bond cleaved by the pump pulse. In the present case of CH2BrI, this is not the case, thus inducing a rotation of the fragment. We discuss the influence of the rotation on the charge transfer process using a classical over-the-barrier model. Our modeling suggests that, despite the fact that the dissociation is slower due to the rotational excitation, the critical interatomic distance for charge transfer is reached faster. Furthermore, we suggest that charge transfer during molecular fragmentation may be modulated in a complex way.

Multiple Sequential Ionization of Valence n = 4 Shell of Krypton by Intense Femtosecond XUV Pulses

Sequential photoionization of krypton by intense extreme ultraviolet femtosecond pulses is studied theoretically for the photon energies below the 3d excitation threshold. This regime with energetically forbidden Auger decay is characterized by special features, such as time scaling of the level population. The model is based on the solution of rate equations with photoionization cross sections of krypton in different charge and multiplet states determined using R-matrix calculations. Predictions of the ion yields and photoelectron spectra for various photon fluence are presented and discussed.

Retrieving intracycle interference in angle-resolved laser-assisted photoemission from argon

We report on a combined experimental and theoretical study of XUV ionization of atomic argon in the presence of a near-infrared (NIR) laser field. Using a table-top source of wavelength-selected femtosecond XUV pulses in combination with a velocity map imaging spectrometer we record angle- and energy-resolved photoelectron distributions and simulate the experimental data by solving the time-dependent Schrödinger equation ab initio. In order to compare with the experimental data we average the calculated energy-angle probability distributions over the experimental focal volume for different values of the magnetic quantum number of the photoelectron. This averaging procedure washes out the intracycle interference pattern, which would otherwise be observed in the form of angular modulations of the photoelectron spectra. We recover these modulations experimentally and in the simulations by evaluating the difference between two averaged distributions that are obtained for slightly different NIR laser field intensities.

Time-Resolved XUV Opacity Measurements of Warm Dense Aluminum.

The free-free opacity in plasmas is fundamental to our understanding of energy transport in stellar interiors and for inertial confinement fusion research. However, theoretical predictions in the challenging dense plasma regime are conflicting and there is a dearth of accurate experimental data to allow for direct model validation. Here we present time-resolved transmission measurements in solid-density Al heated by an XUV free-electron laser. We use a novel functional optimization approach to extract the temperature-dependent absorption coefficient directly from an oversampled pool of single-shot measurements, and find a pronounced enhancement of the opacity as the plasma is heated to temperatures of order of the Fermi energy. Plasma heating and opacity enhancement are observed on ultrafast timescales, within the duration of the femtosecond XUV pulse. We attribute further rises in the opacity on ps timescales to melt and the formation of warm dense matter.

Damage accumulation in thin ruthenium films induced by repetitive exposure to femtosecond XUV pulses below the single-shot ablation threshold

The process of damage accumulation in thin ruthenium films exposed to multiple femtosecond extreme ultraviolet (XUV) free-electron laser (FEL) pulses below the critical angle of reflectance at the FEL facility in Hamburg (FLASH) was experimentally analyzed. The multi-shot damage threshold is found to be lower than the single-shot damage threshold. Detailed analysis of the damage morphology and its dependence on irradiation conditions justifies the assumption that cavitation induced by the FEL pulse is the prime mechanism responsible for multi-shot damage in optical coatings.

Ar 3p photoelectron sideband spectra in two-color XUV + NIR laser fields

We performed photoelectron spectroscopy using femtosecond XUV pulses from a free-electron laser and femtosecond near-infrared pulses from a synchronized laser, and succeeded in measuring Ar 3p photoelectron sideband spectra due to the two-color above-threshold ionization. In our calculations of the first-order time-dependent perturbation theoretical model based on the strong field approximation, the photoelectron sideband spectra and their angular distributions are well reproduced by considering the timing jitter between the XUV and the NIR pulses, showing that the timing jitter in our experiments was distributed over the width of ps. The present approach can be used as a method to evaluate the timing jitter inevitable in FEL experiments.

Photodissociation of aligned CH3I and C6H3F2I molecules probed with time-resolved Coulomb explosion imaging by site-selective extreme ultraviolet ionization.

We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from a free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267 nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon–iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.

Photoelectron angular distribution in two-pathway ionization of neon with femtosecond XUV pulses

We analyze the photoelectron angular distribution in two-pathway interference between non\-resonant one-photon and resonant two-photon ionization of neon. We consider a bichromatic femtosecond XUV pulse whose fundamental frequency is tuned near the $2p^5 3s$ atomic states of neon. The time-dependent Schr\"odinger equation is solved and the results are employed to compute the angular distribution and the associated anisotropy parameters at the main photoelectron line. We also employ a time-dependent perturbative approach, which allows obtaining information on the process for a large range of pulse parameters, including the steady-state case of continuous radiation, i.e., an infinitely long pulse. The results from the two methods are in relatively good agreement over the domain of applicability of perturbation theory.

Free-electron laser multiplex driven by a superconducting linear accelerator.

Free-electron lasers (FELs) generate femtosecond XUV and X-ray pulses at peak powers in the gigawatt range. The FEL user facility FLASH at DESY (Hamburg, Germany) is driven by a superconducting linear accelerator with up to 8000 pulses per second. Since 2014, two parallel undulator beamlines, FLASH1 and FLASH2, have been in operation. In addition to the main undulator, the FLASH1 beamline is equipped with an undulator section, sFLASH, dedicated to research and development of fully coherent extreme ultraviolet photon pulses using external seed lasers. In this contribution, the first simultaneous lasing of the three FELs at 13.4 nm, 20 nm and 38.8 nm is presented.

Role of heat accumulation in the multi-shot damage of silicon irradiated with femtosecond XUV pulses at a 1 MHz repetition rate.

The role played by heat accumulation in multi-shot damage of silicon was studied. Bulk silicon samples were exposed to intense XUV monochromatic radiation of a 13.5 nm wavelength in a series of 400 femtosecond pulses, repeated with a 1 MHz rate (pulse trains) at the FLASH facility in Hamburg. The observed surface morphological and structural modifications are formed as a result of sample surface melting. Modifications are threshold dependent on the mean fluence of the incident pulse train, with all threshold values in the range of approximately 36-40 mJ/cm2. Experimental data is supported by a theoretical model described by the heat diffusion equation. The threshold for reaching the melting temperature (45 mJ/cm2) and liquid state (54 mJ/cm2), estimated from this model, is in accordance with experimental values within measurement error. The model indicates a significant role of heat accumulation in surface modification processes.

Generation of two-color ultra-short radiation pulses from two electron bunches and a chirped seeded free-electron laser

In this paper we describe a new method for the realization of two-color femtosecond radiation pulses in a seeded free-electron laser (FEL). The two-color pulses are obtained from two electron bunches and a chirped seeding laser. Compared to the previous methods based on seeded FELs, our method has the advantages of producing two-color FEL pulses with more flexible tunability both in the pulse durations and separations. Numerical simulations for the Dalian Coherent Light Source confirm that femtosecond XUV pulses with variable pulse durations and time delay can be directly generated from a chirped seed laser at 250nm by using this technique. We also show the possibility of performing a proof-of-principle experiment of this technique based on the Shanghai Deep-Ultraviolet FEL facility.

Time-resolved studies with FELs

Intense femtosecond VUV, XUV, and X-ray pulses from free-electron lasers (FELs) enable time-resolved experiments studying ultrafast dynamics in a large variety of systems relevant, e.g., to physics, chemistry, biology, and material sciences. In this paper, we focus on time-resolved studies of gas-phase molecules, which lie at the crossroad between atomic, molecular and optical physics and ultrafast photochemistry. We describe the current status of the field and discuss typical experimental configurations used for pump-probe experiments with FELs. We illustrate them with three recent examples for such experiments performed at the FLASH and LCLS FELs studying charge transfer following XUV and X-ray photoabsorption as well as photoelectron diffraction from aligned molecules. We conclude with a short outlook on future developments and perspectives for femtosecond pump-probe experiments with FELs.

Ionization and dissociation dynamics of vinyl bromide probed by femtosecond extreme ultraviolet transient absorption spectroscopy

Strong-field induced ionization and dissociation dynamics of vinyl bromide, CH2=CHBr, are probed using femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy. Strong-field ionization is initiated with an intense femtosecond, near infrared (NIR, 775 nm) laser field. Femtosecond XUV pulses covering the photon energy range of 50-72 eV probe the subsequent dynamics by measuring the time-dependent spectroscopic features associated with transitions of the Br (3d) inner-shell electrons to vacancies in molecular and atomic valence orbitals. Spectral signatures are observed for the depletion of neutral C2H3Br, the formation of C2H3Br(+) ions in their ground (X̃) and first excited (Ã) states, the production of C2H3Br(++) ions, and the appearance of neutral Br ((2)P3/2) atoms by dissociative ionization. The formation of free Br ((2)P3/2) atoms occurs on a timescale of 330 ± 150 fs. The ionic à state exhibits a time-dependent XUV absorption energy shift of ∼0.4 eV within the time window of the atomic Br formation. The yield of Br atoms correlates with the yield of parent ions in the à state as a function of NIR peak intensity. The observations suggest that a fraction of vibrationally excited C2H3Br(+) (Ã) ions undergoes intramolecular vibrational energy redistribution followed by the C-Br bond dissociation. The C2H3Br(+) (X̃) products and the majority of the C2H3Br(++) ions are relatively stable due to a deeper potential well and a high dissociation barrier, respectively. The results offer powerful new insights about orbital-specific electronic processes in high field ionization, coupled vibrational relaxation and dissociation dynamics, and the correlation of valence hole-state location and dissociation in polyatomic molecules, all probed simultaneously by ultrafast table-top XUV spectroscopy.

Dual character of excited charge carriers in graphene on Ni(111)

The dynamics of excited charge carriers at the graphene/Ni(111) interface has been investigated by means of time-resolved two-photon photoemission spectroscopy, employing femtosecond-XUV pulses with an energy of 39.2 eV produced by high-order-harmonic generation. Due to the interplay of substrate and adsorbate band structures, the dependence of the lifetimes on the energy $(E\ensuremath{-}{E}_{F})$ of the excited carriers was found to be similar to that of Ni $3d$ electrons measured for clean Ni in the energy range $(E\ensuremath{-}{E}_{F})<1$ eV, while it resembled that of graphite from 1 eV above ${E}_{F}$ onwards. This result is suggested to be the effect of the peculiar electronic structure of the interface, which still possesses features belonging to the pristine graphene layer, such as a residual saddle point.

Tracking the relaxation pathway of photo-excited electrons in 1T-TiSe2

The ultrafast dynamics of excited electrons in 1T-TiSe2 after absorption of a 390 nm light pulse is probed by time- and angle-resolved photoemission spectroscopy using femtosecond XUV pulses. It is demonstrated that the experimental approach can provide a comprehensive view of hot carrier motion in momentum space during relaxation back to equilibrium. This capability opens a new avenue in the investigation of energy dissipation processes in solids after intense optical excitation.

Investigation of damage induced by intense femtosecond XUV pulses in silicon crystals by means of white beam synchrotron section topography

Silicon crystalline samples were exposed to intense single pulses of XUV radiation (λ=13.5nm) what lead to melting and ablation of the surface material. The deformation field around craters along the whole thickness of silicon wafers was observed by means of the synchrotron transmission section topography using the beam perpendicular to the surface of the sample. The geometrical shape and depth extension around craters was evaluated based on numerous, dense series of section topographs spaced by 10µm. In the topographs we observed the direct image connected with the boundary of the crater associated with some deformation of the Kato fringes. The evaluated depth extension, different for individual craters, was in the range of 30–100µm. The depth values were confirmed also by evaluations based on the Bragg case section topographs.It was possible to reproduce the contrast of the craters in transmission section topographs by numerical simulation based on integration of the Takagi–Taupin equations. The damage of the crystal defects connected with craters was approximated as droplet-like inclusions.

Ultrafast Relaxation Dynamics of Highly-excited States in N2Molecules Excited by Femtosecond XUV Pulses

We used velocity-map-imaging to measure electronic and nuclear dynamics in N2 molecules excited by a train of attosecond pulses. A time-to-space mapping of autoionization channel is demonstrated. It is found that the autoionization becomes energetically allowed when the two nuclei are still very close (~ 3 A) and that it can be coherently manipulated by a strong femtosecond infrared pulse.

Molecular frame photoemission in dissociative ionization of H2 and D2 induced by high harmonic generation femtosecond XUV pulses

We report the first results of molecular frame photoelectron emission for dissociative photoionization (DPI) of H2 and D2 molecules induced by a spectrally filtered single high harmonic of a few femtosecond duration, using coincident electron–ion velocity vector correlation techniques. For the studied photon energies around 32 eV, where the resonant excitation of the Q1 and Q2 doubly excited states occurs, autoionization and nuclear dynamics are coupled on a few femtosecond timescale, giving rise to quantum interferences. Molecular frame photoelectron angular distributions (MFPADs), traced as a function of the kinetic energy release of the atomic fragments, provide the most sensitive observables for such complex dynamics. These results compare well with recent spectrally resolved experiments using synchrotron radiation which are also reported. As a novel XUV light source running at multi-kHz repetition rate and synchronized with laser pulses, high-order harmonic generation (HHG) opens new possibilities for extending these investigations to time-resolved studies at the femtosecond scale.

Electron Correlation in Real Time

Electron correlation, caused by the interaction among electrons in a multielectron system, manifests itself in all states of matter. A complete theoretical description of interacting electrons is challenging; different approximations have been developed to describe the fundamental aspects of the correlation that drives the evolution of simple (few-electron systems in atoms/molecules) as well as complex (multielectron wave functions in atoms, molecules, and solids) systems. Electron correlation plays a key role in the relaxation mechanisms that characterize excited states of neutral or ionized atoms and molecules populated by absorption of extreme ultraviolet (XUV) or X-ray radiation. The dynamics of these states can lead to different processes such as Fano resonance and Auger decay in atoms or interatomic Coulombic decay or charge migration in molecules and clusters. Many of these relaxation mechanisms are ubiquitous in nature and characterize the interaction of complex systems, such as biomolecules, adsorbates on surfaces, and hydrogen-bonded clusters, with XUV light. These mechanisms evolve typically on the femtosecond (1 fs=10(-15) s) or sub-femtosecond timescale. The experimental availability of few-femtosecond and attosecond (1 as=10(-18) s) XUV pulses achieved in the last 10 years offers, for the first time, the opportunity to excite and probe in time these dynamics giving the possibility to trace and control multielectron processes. The generation of ultrashort XUV radiation has triggered the development and application of spectroscopy techniques that can achieve time resolution well into the attosecond domain, thereby offering information on the correlated electronic motion and on the correlation between electron and nuclear motion. A deeper understanding of how electron correlation works could have a large impact in several research fields, such as biochemistry and biology, and trigger important developments in the design and optimization of electronic devices.

XUV ionization of aligned molecules

New extreme-ultraviolet (XUV) light sources such as high-order-harmonic generation (HHG) and free-electron lasers (FELs), combined with laser-induced alignment techniques, enable novel methods for making molecular movies based on measuring molecular frame photoelectron angular distributions. Experiments are presented where CO2 molecules were impulsively aligned using a near-infrared laser and ionized using femtosecond XUV pulses obtained by HHG. Measured electron angular distributions reveal contributions from four orbitals and the onset of the influence of the molecular structure.