Ultraviolet Free-electron Laser Research Articles

Bridging the gap of storage ring light sources and linac-driven free-electron lasers

High-gain free-electron lasers (FELs) are driven by short, high-charge density electron beams as only produced at dedicated single pass or recirculating linear accelerators. We describe new conceptual, technical, and modeling solutions to produce subpicosecond, up to $\ensuremath{\sim}100\text{ }\text{ }\ensuremath{\mu}\mathrm{J}$-energy extreme ultra-violet and soft x-ray FEL pulses at high- and tunable repetition rates, from diffraction-limited storage ring light source. In contrast to previously proposed schemes, we show that lasing can be simultaneous to the standard multibunch radiation emission from short insertion devices, and that it can be obtained with limited impact on the storage ring infrastructure. By virtue of the high-average power but moderate pulse energy, the storage ring-driven high-gain FEL would open the door to unprecedented accuracy in time-resolved spectroscopic analysis of matter in the linear response regime, in addition to inelastic scattering experiments.

Photodissociation Dynamics of H2O via the Ẽ' (1B2) Electronic State.

Photodissociation dynamics of H2O via the Ẽ'1B2 state were studied using the high-resolution H atom photofragment translational spectroscopy method, in combination with the tunable vacuum ultraviolet free electron laser (VUV FEL). The measured translational energy spectra allow us to determine the respective quantum state population distributions for the nascent OH(X2Π) and OH(A2Σ+) photofragments. Analyses of the quantum state population distributions show both the ground and electronically excited OH fragments to be formed with moderate vibrational excitation but with highly rotational excitation. Unlike the dissociation via the lower-lying electronic states, where OH(X) is the major fragment, the OH(A) products are predominant via the Ẽ' state. These products are mainly ascribed to a fast dissociation on the B̃1A1 state surface after nonadiabatic transitions from the initial excited Ẽ' state to the B̃ state. Meanwhile, another dissociation pathway from the Ẽ' state to the 1B2 3pb2 state, followed by coupling to the 1A2 3pb2 state, is also observed, which yields the OH(X) + H and O(3P) + 2H products.

Ultrafast Resonant Interatomic Coulombic Decay Induced by Quantum Fluid Dynamics

When weakly-bound complexes are multiply excited by intense electromagnetic radiation, energy can be exchanged between neighboring atoms through a type of resonant interatomic Coulombic decay (ICD). This decay mechanism due to multiple excitations has been predicted to be relatively slow, typically lasting tens to hundreds of picoseconds. Here, we directly measure the ICD timescale in resonantly excited helium droplets using a high resolution, tunable, extreme ultraviolet free electron laser. Over an extensive range of droplet sizes and laser intensities, we discover the decay to be surprisingly fast, with decay times as fast as 400 femtoseconds, and to only present a weak dependence on the density of the excited states. Using a combination of time dependent density functional theory and ab initio quantum chemistry calculations, we elucidate the mechanisms of this ultrafast decay process where pairs of excited helium atoms in one droplet strongly attract each other and form merging void bubbles which drastically accelerates ICD.

All-optical single-shot complete electric field measurement of extreme ultraviolet free electron laser pulses

Recent advances in ultrafast extreme ultraviolet (EUV) and x-ray light sources provide direct access to fundamental time and length scales for biology, chemistry, and materials physics. However, such light pulses are challenging to measure due to the need for femtosecond time resolution at difficult-to-detect wavelengths. Also, single-shot measurements are needed because severe pulse-to-pulse fluctuations are common. Here we demonstrate single-shot, complete field measurements by applying a novel version of frequency resolved optical gating. An EUV free electron laser beam creates a transient grating containing the pulse’s electric field information, which is read out with a 400 nm probe pulse. By varying the time delay between two copies of the EUV pump, rather than between the pump and the probe, we separate the needed coherent wave mixing from the slow incoherent response. Because this approach uses photoionization, it should be applicable from the vacuum ultraviolet to hard x rays.

Vibrational Signature of Dynamic Coupling of a Strong Hydrogen Bond.

Elucidating the dynamic couplings of hydrogen bonds remains an important and challenging goal for spectroscopic studies of bulk systems, because their vibrational signatures are masked by the collective effects of the fluctuation of many hydrogen bonds. Here we utilize size-selected infrared spectroscopy based on a tunable vacuum ultraviolet free electron laser to unmask the vibrational signatures for the dynamic couplings in neutral trimethylamine-water and trimethylamine-methanol complexes, as microscopic models with only one single hydrogen bond holding two molecules. Surprisingly broad progression of OH stretching peaks with distinct intensity modulation over ∼700 cm-1 is observed for trimethylamine-water, while the dramatic reduction of this progression in the trimethylamine-methanol spectrum offers direct experimental evidence for the dynamic couplings. State-of-the-art quantum mechanical calculations reveal that such dynamic couplings are originated from strong Fermi resonance between the stretches of hydrogen-bonded OH and several motions of the solvent water/methanol, such as translation, rocking, and bending, which are significant in various solvated complexes commonly found in atmospheric and biological systems.

Infrared spectroscopy of neutral clusters based on a vacuum ultraviolet free electron laser

Spectroscopic characterization of clusters is crucial to understanding the structures and reaction mechanisms at the microscopic level, but it has been proven to be a grand challenge for neutral clusters because the absence of a charge makes it difficult for the size selection and detection. Infrared (IR) spectroscopy based on threshold photoionization using a tunable vacuum ultraviolet free electron laser (VUV-FEL) has recently been developed in the lab. The IR-VUV depletion and IR+VUV enhancement spectroscopic techniques open new avenues for size-selected IR spectroscopies of a large variety of neutral clusters without confinement (i.e., an ultraviolet chromophore, a messenger tag, or a host matrix). The spectroscopic principles have been demonstrated by investigations of some neutral water clusters and some metal carbonyls. Here, the spectroscopic principles and their applications for neutral clusters are reviewed.

Infrared spectroscopic study of hydrogen bonding topologies in the smallest ice cube

The water octamer with its cubic structure consisting of six four-membered rings presents an excellent cluster system for unraveling the cooperative interactions driven by subtle changes in the hydrogen-bonding topology. Despite prediction of many distinct structures, it has not been possible to extract the structural information encoded in their vibrational spectra because this requires size-selectivity of the neutral clusters with sufficient resolution to identify the contributions of the different isomeric forms. Here we report the size-specific infrared spectra of the isolated cold, neutral water octamer using a scheme based on threshold photoionization using a tunable vacuum ultraviolet free electron laser. A plethora of sharp vibrational bands features are observed. Theoretical analysis of these patterns reveals the coexistence of five cubic isomers, including two with chirality. The relative energies of these structures are found to reflect topology-dependent, delocalized multi-center hydrogen-bonding interactions. These results demonstrate that even with a common structural motif, the degree of cooperativity among the hydrogen-bonding network creates a hierarchy of distinct species. The implications of these results on possible metastable forms of ice are speculated.

Time-resolved site-selective imaging of predissociation and charge transfer dynamics: the CH3I B-band

The predissociation dynamics of the 6s (B2E) Rydberg state of gas-phase CH3I were investigated by time-resolved Coulomb-explosion imaging using extreme ultraviolet (XUV) free-electron laser pulses. Inner-shell ionization at the iodine 4d edge was utilized to provide a site-specific probe of the ensuing dynamics. The combination of a velocity-map imaging (VMI) spectrometer coupled with the pixel imaging mass spectrometry (PImMS) camera permitted three-dimensional ionic fragment momenta to be recorded simultaneously for a wide range of iodine charge states. In accord with previous studies, initial excitation at 201.2 nm results in internal conversion and subsequent dissociation on the lower-lying A-state surface on a picosecond time scale. Examination of the time-dependent yield of low kinetic energy iodine fragments yields mechanistic insights into the predissociation and subsequent charge transfer following multiple ionization of the iodine products. The effect of charge transfer was observed through differing delay-dependencies of the various iodine charge states, from which critical internuclear distances for charge transfer could be inferred and compared to a classical over-the-barrier model. Time-dependent photofragment angular anisotropy parameters were extracted from the central slice of the Newton sphere, without Abel inversion, and highlight the effect of rotation of the parent molecule before dissociation, as observed in previous works. Our results demonstrate the ability to perform three-dimensional ion imaging at high event rates and showcase the potential benefits of this approach, particularly in relation to further time-resolved studies at free-electron laser facilities.

Electronically Excited OH Super-rotors from Water Photodissociation by Using Vacuum Ultraviolet Free-Electron Laser Pulses.

The fragmentation dynamics of water in a superexcited state play an important role in the ionosphere of the planets and in the photodissociation region (PDR) of the planetary nebula. In this Letter, we experimentally study the fragmentation dynamics of H2O with the energy above its ionization potential initiated by vacuum ultraviolet free-electron laser pulses. The experimental results indicate that the binary fragmentation channels H + OH and the triple channels O + 2H both present at 96.4 nm photolysis. Electronically excited OH super-rotors (v = 0, N ≥ 36, or v = 1, N ≥ 34), with the internal energy just above the OH (A) dissociation energy, are observed for the first time, which are only supported by the large centrifugal barriers. An absolute cross section of these super-rotors is estimated to be 0.7(±0.3) × 10-18 cm2. The tunnelling rates of these extremely rotationally excited states are also analyzed. This work shows a spectacular example of energy transfer from a photon to fragment rotation through photodissociation.

Tracking the ultraviolet-induced photochemistry of thiophenone during and after ultrafast ring opening.

Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free-electron laser to trace the ultrafast ring opening of gas-phase thiophenone molecules following ultraviolet photoexcitation. When combined with ab initio electronic structure and molecular dynamics calculations of the excited- and ground-state molecules, the results provide insights into both the electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state are shown to be driven by ballistic S-C bond extension and to be complete within 350 fs. Theory and experiment also enable visualization of the rich ground-state dynamics that involve the formation of, and interconversion between, ring-opened isomers and the cyclic structure, as well as fragmentation over much longer timescales.

Coherent, high repetition rate tender x-ray free-electron laser seeded by an extreme ultra-violet free-electron laser oscillator

A seeded FEL driven by a linac based on super conducting cavities, generating 108–1010 coherent photons per shot at 2–5 keV with 0.2–1 MHz of repetition rate, can address the need of a source devoted to fine analysis of matter using the linear spectroscopy technique. The seeding scheme described hereafter is a multi-stage cascade upshifting the radiation frequency by a factor 20–40. The x-ray range can be achieved with a seed constituted by a coherent flash in the extreme ultraviolet range provided by an FEL oscillator operating at 12–14 nm. The whole chain of x-ray generation is described by means of start-to-end three-dimensional simulations.

Infrared spectroscopy of neutral water clusters at finite temperature: Evidence for a noncyclic pentamer

Infrared spectroscopic study of neutral water clusters is crucial to understanding of the hydrogen-bonding networks in liquid water and ice. Here we report infrared spectra of size-selected neutral water clusters, (H2O) n (n = 3-6), in the OH stretching vibration region, based on threshold photoionization using a tunable vacuum ultraviolet free-electron laser. Distinct OH stretch vibrational fundamentals observed in the 3,500-3,600-cm-1 region of (H2O)5 provide unique spectral signatures for the formation of a noncyclic pentamer, which coexists with the global-minimum cyclic structure previously identified in the gas phase. The main features of infrared spectra of the pentamer and hexamer, (H2O) n (n = 5 and 6), span the entire OH stretching band of liquid water, suggesting that they start to exhibit the richness and diversity of hydrogen-bonding networks in bulk water.

Multielectron-Ion Coincidence Spectroscopy of Xe in Extreme Ultraviolet Laser Fields: Nonlinear Multiple Ionization via Double Core-Hole States.

Ultrafast multiphoton ionization of Xe in strong extreme ultraviolet free-electron laser (FEL) fields (91eV, 30fs, 1.6×10^{12} W/cm^{2}) has been investigated by multielectron-ion coincidence spectroscopy. The electron spectra recorded in coincidence with Xe^{4+} show characteristic features associated with two-photon absorption to the 4d^{-2} double core-hole (DCH) states and subsequent Auger decay. It is found that the pathway via the DCH states, which has eluded clear identification in previous studies, makes a large contribution to the multiple ionization, despite the long FEL pulse duration compared with the lifetime of the 4d core-hole states.

Investigation of cross luminescence in lanthanum fluoride as a potential fast-response scintillator

We report the potential of lanthanum fluoride (LaF3) as a fast-response scintillator. When excited by an extreme ultraviolet free electron laser, neodymium-doped LaF3 (Nd3+:LaF3) exhibited a 1.9 ns fast decay component and a 6.7 ns slow decay component for its 172 nm emission peak. The slow decay component is due to interconfigurational 4f25d-4f3 transition in Nd3+. First principles density functional theory calculations using the Perdew–Burke–Ernzerhof hybrid functional including exact exchange (PBE0) and the Green’s function and screened Coulomb interaction (GW) approximation as implemented in the Vienna Ab initio Simulation Package using plane-wave basis sets within the projector-augmented wave method elucidate the electronic structure of LaF3 and reveal that the fast decay component could be due to partial cross luminescence (CL) from the bottom of the valence band to the top of the outermost core band. The presence of CL alludes to the potential of LaF3 as a fast-response scintillator.

Application of laser dispersion method in apparatus combining H atom Rydberg tagging time-of-flight technique with vacuum ultraviolet free electron laser

Photodissociation of H2S in the VUV region plays an important role in the atmospheric chemistry and interstellar chemistry. To date, however, few studies have been focused on this topic. In this article, we have described a laser dispersion method applied in the apparatus combining the high-n H atom Rydberg tagging time-of-flight technique with the vacuum ultraviolet free electron laser (VUV FEL). The Lyman-α laser beam (121.6 nm) used in the H-atom detection was generated by the difference frequency four-wave mixing schemes in a Kr/Ar gas cell. After passing through an off-axis biconvex LiF lens, the 121.6 nm beam was dispersed from the 212.6 nm and 845 nm beams due to the different deflection angles experienced by these laser beams at the surfaces of the biconvex lens. This method can eliminate the background signal from the 212.6 nm photolysis. Combined with the VUV FEL, photodissociation of H2S at 122.95 nm was studied successfully. The TOF spectrum was measured and the derived total kinetic energy release spectrum was displayed. The results suggest that the experimental setup is a powerful tool for investigating photodissociation dynamics of molecules in the VUV region which involves the H-atom elimination processes.

Infrared + vacuum ultraviolet two-color ionization spectroscopy of neutral metal complexes based on a tunable vacuum ultraviolet free-electron laser.

This paper describes an experimental technique for studying neutral metal complexes using infrared + vacuum ultraviolet (IR+VUV) two-color ionization spectroscopy based on a tunable VUV free-electron laser (VUV-FEL). The preliminary IR spectroscopy results of mass-selected nickel tetracarbonyl are reported in this work. The results demonstrate that the tunable VUV-FEL light allows the selective ionization of a given neutral cluster free of confinement along with the recording of well-resolved IR spectra. As the ionization energies of many neutral clusters are accessible by a broadly tunable VUV-FEL (50-150 nm) and near-threshold ionization can be readily achieved, the proposed experimental method offers unique possibilities for the size-specific study of a wide variety of confinement-free neutral clusters.

Infrared Spectroscopy of Neutral Water Dimer Based on a Tunable Vacuum Ultraviolet Free Electron Laser

Infrared (IR) spectroscopy provides detailed structural and dynamical information on clusters at the fingerprint level. Herein, we demonstrate the capability of a tunable vacuum ultraviolet free electron laser (VUV-FEL) for selective detection of a wide variety of neutral water clusters and for recording the size-dependent IR spectra. The present technique does not require the presence of an ultraviolet chromophore or a dipole moment and is generally applicable for IR spectroscopy of neutral clusters free from confinement. To show the features of our technique, we report here the IR spectra of neutral water dimer in the OH stretch region, providing benchmarks for theoretical study of the accurate description of hydrogen bonding structures involved in liquid water and ice. Quantum mechanical calculations on a 12-dimensional ab initio potential energy surface are utilized to simulate the anharmonic vibrational spectra of water dimer. These results help to resolve the controversy of the exact vibrational assignment of each band feature of the water dimer.

The theoretical study of terahertz-streaking photoionization for ultrafast imaging of density matrix in rubidium atom

Terahertz-streaking photoionization can be exploited to resolve ultrafast quantum beating and reconstruct the ultrafast evolution of density matrix. Here, we propose an experimental strategy to implement the method merely with the tabletop femtosecond system and magneto-optical trap reaction microscopy. The probe pulse consists of an ultraviolet pulse with pulse duration of about 30 fs and a strong terahertz pulse with strength of about 2.6 fs in rubidium-atom superposition. The population and coherence terms of the density matrix can be projected into different positions of the photoelectron momentum distribution. The reconstruction algorithm was designed to acquire the ultrafast evolution of density matrix from the time-dependent photoelectron spectrum. The experimental conception can demonstrate the newly proposed transient spectral method only with the commercial femtosecond laser system and magneto-optical trap reaction microscopy, thus preventing the complex laser system, such as extreme ultraviolet free electron lasers and attosecond higher harmonics, allowing a new metrology to explore the coherence dynamics of quantum systems.

Intense VUV–xenon-cluster interaction revisited

During the inaugural experiment at FLASH, the first vacuum ultraviolet (VUV) free-electron laser facility, Wabnitz et al. [Nature 420, 482 (2002)] irradiated xenon clusters and sparked a concerted theoretical and experimental effort to understand how dense, finite plasmas behave under intense irradiation. In this work, we revisit this experiment with a model that is based only on well-established atomic processes. We find that the experimental results can be explained by hybrid quantum-classical molecular-dynamics simulations if collisional excitation, recombination, and a sufficiently deep soft-core potential is used. Our recent theoretical model for inverse bremsstrahlung heating (IBH) is used to show that the measured energy absorbed by the cluster in the experiment is well predicted by our model.

Short-wavelength four wave mixing experiments using single and two-color schemes at FERMI

The development of ultra-bright extreme ultraviolet (EUV) and X-ray free electron laser (FEL) sources has enabled the extension of wave-mixing approaches into the short wavelength regime. Such a class of experiments relies upon nonlinear interactions among multiple light pulses offering a unique tool for exploring the dynamics of ultrafast processes and correlations between selected excitations at relevant length and time scales adding elemental and site selectivity as well. Besides the availability of a suitable photon source, the implementation of wave mixing methodology requires efforts in developing the instrumental set-up. We have realized at the FERMI FEL two dedicated set-ups to handle multiple FEL beams with preselected parameters in a non-collinear fashion and control their interaction sequence at the target. These unique apparatuses, combined with the exceptional characteristics of the seeded FERMI FEL, have allowed us to make the first steps into this field and further advances are foreseen in the near future.