Millijoule Femtosecond X-Ray Pulses from an Efficient Fresh-Slice Multistage Free-Electron Laser.

We present the generation of x-ray pulses with average pulse energies up to one millijoule and rms pulse durations down to the femtosecond level. We have produced these intense and short pulses by employing the fresh-slice multistage amplification scheme with a transversely tilted electron beam in a free-electron laser. In this scheme, a short pulse is produced in the first stage and later amplified by fresh parts of the electron bunch in up to a total of four stages of amplification. Our implementation is efficient, since practically the full electron beam contributes to produce the x-ray pulse. Our implementation is also compact, utilizing only 32 m of undulator. The demonstration was done at Athos, the soft x-ray beamline of SwissFEL, which was designed with high flexibility to take full advantage of the multistage amplification scheme. It opens the door for scientific opportunities following ultrafast dynamics using nonlinear x-ray spectroscopy techniques or avoiding electronic damage when capturing structures with a single intense pulse via single-particle imaging.

An X-ray free-electron laser with a highly configurable undulator and integrated chicanes for tailored pulse properties.

X-ray free-electron lasers (FELs) are state-of-the-art scientific tools capable to study matter on the scale of atomic processes. Since the initial operation of X-ray FELs more than a decade ago, several facilities with upgraded performance have been put in operation. Here we present the first lasing results of Athos, the soft X-ray FEL beamline of SwissFEL at the Paul Scherrer Institute in Switzerland. Athos features an undulator layout based on short APPLE-X modules providing full polarisation control, interleaved with small magnetic chicanes. This versatile configuration allows for many operational modes, giving control over many FEL properties. We show, for example, a 35% reduction of the required undulator length to achieve FEL saturation with respect to standard undulator configurations. We also demonstrate the generation of more powerful pulses than the ones obtained in typical undulators. Athos represents a fundamental step forward in the design of FEL facilities, creating opportunities in FEL-based sciences.

Direct tracking of ultrafast proton transfer in water dimers.

Upon ionization, water forms a highly acidic radical cation H2O+· that undergoes ultrafast proton transfer (PT)-a pivotal step in water radiation chemistry, initiating the production of reactive H3O+, OH[Formula: see text] radicals, and a (hydrated) electron. Until recently, the time scales, mechanisms, and state-dependent reactivity of ultrafast PT could not be directly traced. Here, we investigate PT in water dimers using time-resolved ion coincidence spectroscopy applying a free-electron laser. An extreme ultraviolet (XUV) pump photon initiates PT, and only dimers that have undergone PT at the instance of the ionizing XUV probe photon result in distinct H3O+ + OH+ pairs. By tracking the delay-dependent yield and kinetic energy release of these ion pairs, we measure a PT time of (55 ± 20) femtoseconds and image the geometrical rearrangement of the dimer cations during and after PT. Our direct measurement shows good agreement with nonadiabatic dynamics simulations for the initial PT and allows us to benchmark nonadiabatic theory.

A compact gas attenuator for the SwissFEL ATHOS beamline realized using additive manufacturing.

Gas attenuators are important devices providing accurate variation of photon intensity for soft X-ray beamlines. In the SwissFEL ATHOS beamline front-end the space is very limited and an innovative approach has been taken to provide attenuation of three orders of magnitude up to an energy of 1200 eV. Additive manufacturing of a differential pumping system vacuum manifold allowed a triple pumping stage to be realized in a space of less than half a meter. Measurements have shown that the response of the device is as expected from theoretical calculations.

Ultrafast Single-Particle Imaging with Intense X-Ray Pulses.

Ultrafast single-particle imaging with intense x-ray pulses from free-electron laser sources provides a new approach for visualizing structure and dynamics on the nanoscale. After a short introduction to the novel free-electron laser sources and methods, we highlight selected applications and discuss how ultrafast imaging flourishes from method development to early applications in physics and biology to opportunities for chemical sciences.

Generation and simple characterization of flat, liquid jets.

We present an approach to determine the absolute thickness profile of flat liquid jets, which takes advantage of the information of thin film interference combined with light absorption, both captured in a single microscopic image. The feasibility of the proposed method is demonstrated on our compact experimental setup used to generate micrometer thin, free-flowing liquid jet sheets upon collision of two identical laminar cylindrical jets. Stable operation was achieved over several hours of the flat jet in vacuum (10-4 mbar), making the system ideally suitable for soft x-ray photon spectroscopy of liquid solutions. We characterize the flat jet size and thickness generated with two solvents, water and ethanol, employing different flow rates and nozzles of variable sizes. Our results show that a gradient of thickness ranging from a minimal thickness of 2 µm to over 10 µm can be found within the jet surface area. This enables the tunability of the sample thickness in situ, allowing the optimization of the transmitted photon flux for the chosen photon energy and sample. We demonstrate the feasibility of x-ray absorption spectroscopy experiments in transmission mode by measuring at the oxygen K-edge of ethanol. Our characterization method and the description of the experimental setup and its reported performance are expected to expand the range of applications and facilitate the use of flat liquid jets for spectroscopy experiments.

Intermolecular Coulombic Decay in Endohedral Fullerene at the 4d→4f Resonance.

Intermolecular processes offer unique decay mechanisms for complex systems to internally relax. Here, we report the observation of an intermolecular Coulombic decay channel in an endohedral fullerene, a holmium nitride complex (Ho_{3}N) embedded within a C_{80} fullerene, between neighboring holmium ions, and between the holmium complex and the carbon cage. By measuring the ions and the electrons in coincidence after XUV photoabsorption, we can isolate the different decay channels, which are found to be more prevalent relative to intra-atomic Auger decay.

X-ray diffractive imaging of controlled gas-phase molecules: Toward imaging of dynamics in the molecular frame.

We report experimental results on the diffractive imaging of three-dimensionally aligned 2,5-diiodothiophene molecules. The molecules were aligned by chirped near-infrared laser pulses, and their structure was probed at a photon energy of 9.5 keV (λ ≈ 130 pm) provided by the Linac Coherent Light Source. Diffracted photons were recorded on the Cornell-SLAC pixel array detector, and a two-dimensional diffraction pattern of the equilibrium structure of 2,5-diiodothiophene was recorded. The retrieved distance between the two iodine atoms agrees with the quantum-chemically calculated molecular structure to be within 5%. The experimental approach allows for the imaging of intrinsic molecular dynamics in the molecular frame, albeit this requires more experimental data, which should be readily available at upcoming high-repetition-rate facilities.

Photo-ionization and fragmentation of Sc3N@C80 following excitation above the Sc K-edge.

We have investigated the ionization and fragmentation of a metallo-endohedral fullerene, Sc3N@C80, using ultrashort (10 fs) x-ray pulses. Following selective ionization of a Sc (1s) electron (hν = 4.55 keV), an Auger cascade leads predominantly to either a vibrationally cold multiply charged parent molecule or multifragmentation of the carbon cage following a phase transition. In contrast to previous studies, no intermediate regime of C2 evaporation from the carbon cage is observed. A time-delayed, hard x-ray pulse (hν = 5.0 keV) was used to attempt to probe the electron transfer dynamics between the encapsulated Sc species and the carbon cage. A small but significant change in the intensity of Sc-containing fragment ions and coincidence counts for a delay of 100 fs compared to 0 fs, as well as an increase in the yield of small carbon fragment ions, may be indicative of incomplete charge transfer from the carbon cage on the sub-100 fs time scale.

Tracing charge transfer in argon dimers by XUV-pump IR-probe experiments at FLASH.

Charge transfer (CT) at avoided crossings of excited ionized states of argon dimers is observed using a two-color pump-probe experiment at the free-electron laser in Hamburg (FLASH). The process is initiated by the absorption of three 27-eV-photons from the pump pulse, which leads to the population of Ar2+*-Ar states. Due to nonadiabatic coupling between these one-site doubly ionized states and two-site doubly ionized states of the type Ar+*-Ar+, CT can take place leading to the population of the latter states. The onset of this process is probed by a delayed infrared (800 nm) laser pulse. The latter ionizes the dimers populating repulsive Ar2+ -Ar+ states, which then undergo a Coulomb explosion. From the delay-dependent yields of the obtained Ar2+ and Ar+ ions, the lifetime of the charge-transfer process is extracted. The obtained experimental value of (531 ± 136) fs agrees well with the theoretical value computed from Landau-Zener probabilities.

A coincidence velocity map imaging spectrometer for ions and high-energy electrons to study inner-shell photoionization of gas-phase molecules.

We report on the design and performance of a double-sided coincidence velocity map imaging spectrometer optimized for electron-ion and ion-ion coincidence experiments studying inner-shell photoionization of gas-phase molecules with soft X-ray synchrotron radiation. The apparatus employs two microchannel plate detectors equipped with delay-line anodes for coincident, time- and position-resolved detection of photoelectrons and Auger electrons with kinetic energies up to 300 eV on one side of the spectrometer and photoions up to 25 eV per unit charge on the opposite side. We demonstrate its capabilities by measuring valence photoelectrons and ion spectra of neon and nitrogen and by studying channel-resolved photoelectron and Auger spectra along with fragment-ion momentum correlations for chlorine 2p inner-shell ionization of cis- and trans-1,2-dichloroethene.

Reaction microscope endstation at FLASH2.

A reaction microscope dedicated to multi-particle coincidence spectroscopy on gas-phase samples is installed at beamline FL26 of the free-electron laser FLASH2 in Hamburg. The main goals of the instrument are to follow the dynamics of atoms, molecules and small clusters on their natural time-scale and to study non-linear light-matter interaction with such systems. To this end, the reaction microscope is combined with an in-line extreme-ultraviolet (XUV) split-delay and focusing optics, which allows time-resolved XUV-XUV pump-probe spectroscopy to be performed.

Tracing the 267 nm-Induced Radical Formation in Dimethyl Disulfide Using Time-Resolved X-ray Absorption Spectroscopy.

Disulfide bonds are pivotal for the structure, function, and stability of proteins, and understanding ultraviolet (UV)-induced S-S bond cleavage is highly relevant for elucidating the fundamental mechanisms underlying protein photochemistry. Here, the near-UV photodecomposition mechanisms in gas-phase dimethyl disulfide, a prototype system with a S-S bond, are probed by ultrafast transient X-ray absorption spectroscopy. The evolving electronic structure during and after the dissociation is simultaneously monitored at the sulfur L1,2,3-edges and the carbon K-edge with 100 fs (FWHM) temporal resolution using the broadband soft X-ray spectrum from a femtosecond high-order harmonics light source. Dissociation products are identified with the help of ADC and RASPT2 electronic-structure calculations. Rapid dissociation into two CH3S radicals within 120 ± 30 fs is identified as the major relaxation pathway after excitation with 267 nm radiation. Additionally, a 30 ± 10% contribution from asymmetric CH3S2 + CH3 dissociation is indicated by the appearance of CH3 radicals, which is, however, at least partly the result of multiphoton excitation.

Terahertz-Field-Induced Time Shifts in Atomic Photoemission.

Time delays for atomic photoemission obtained in streaking or reconstruction of attosecond bursts by interference of two-photon transitions experiments originate from a combination of the quantum mechanical Wigner time and the Coulomb-laser coupling. While the former was investigated intensively theoretically as well as experimentally, the latter attracted less interest in experiments and has mostly been subject to calculations. Here, we present a measurement of the Coulomb-laser coupling-induced time shifts in photoionization of neon at 59.4 eV using a terahertz (THz) streaking field (λ=152 µm). Employing a reaction microscope at the THz beamline of the free-electron laser in Hamburg (FLASH), we have measured relative time shifts of up to 70 fs between the emission of 2p photoelectrons (∼38 eV) and low-energetic (<1 eV) photoelectrons. A comparison with theoretical predictions on Coulomb-laser coupling reveals reasonably good agreement.

Electron-Withdrawing Effects in the Photodissociation of CH2ICl To Form CH2Cl Radical, Simultaneously Viewed Through the Carbon K and Chlorine L2,3 X-ray Edges.

A fundamental chlorine-containing radical, CH2Cl, is generated by the ultrafast photodissociation of CH2ICl at 266 nm and studied at both the carbon K edge (∼284 eV) and chlorine L2,3 edge (∼200 eV) by femtosecond X-ray transient absorption spectroscopy. The electronic structure of CH2Cl radical is characterized by a prominent new carbon 1s X-ray absorption feature at lower energy, resulting from a transition to the half-filled frontier carbon 2p orbital (singly occupied molecular orbital of the radical; SOMO). Shifts of other core-to-valence absorption features upon photodissociation of CH2ICl to yield ·CH2Cl indicate changes in the energies of core-level transitions of carbon and chlorine to the σ*(C-Cl) valence orbital. When the C-I bond breaks, loss of the electron-withdrawing iodine atom donates electron density back to carbon and shields the carbon 1s core level, resulting in a ∼0.8 eV red shift of the carbon 1s to σ*(C-Cl) transition. Meanwhile, the 2p inner shell of the chlorine atom in the radical is less impacted by the iodine atom removal, as demonstrated by the observation of a ∼0.6 eV blue shift of the transitions at the chlorine L2,3 edges, mainly due to the stronger C-Cl bond and the increased energy of the σ*(C-Cl) orbital. The results suggest that the shift in the carbon 1s orbital is greater than the shift in the σ*(C-Cl) orbital upon going from the closed-shell molecule to the radical. Ab initio calculations using the equation of motion coupled-cluster theory establish rigorous assignment and positions of the X-ray spectral features in the parent molecule and the location of the SOMO in the CH2Cl radical.

Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X-ray Transient Absorption Spectroscopy.

The ultraviolet-induced photochemistry of five-membered heterocyclic rings often involves ring opening as a prominent excited-state relaxation pathway. The identification of this particular photoinduced mechanism, however, presents a challenge for many experimental methods. We show that femtosecond X-ray transient absorption spectroscopy at the carbon K-edge (∼284 eV) provides core-to-valence spectral fingerprints that enable the unambiguous identification of ring-opened isomers of organic heterocycles. The unique differences in the electronic structure between a carbon atom bonded to the oxygen in the ring versus a carbon atom set free of the oxygen in the ring-opened product are readily apparent in the X-ray spectra. Ultrafast ring opening via C-O bond fission occurs within ∼350 fs in 266-nm photoexcited furfural, as evidenced by fingerprint core (carbon 1s) electronic transitions into a nonbonding orbital of the open-chain carbene intermediate at 283.3 eV. The lack of recovery of the 1sπ* ground-state depletion in furfural at 286.4 eV indicates that internal conversion to the ground state is a minor channel. These experimental results, augmented by recent advances in the generation of isolated attosecond pulses at the carbon K-edge, will pave the way for probing ring-opened conical intersection dynamics in the future.

Ultrafast Intersystem Crossing in Acetylacetone via Femtosecond X-ray Transient Absorption at the Carbon K-Edge.

Molecular triplet states constitute a crucial gateway in the photochemical reactions of organic molecules by serving as a reservoir for the excess electronic energy. Here, we report the remarkable sensitivity of soft X-ray transient absorption spectroscopy for following the intricate electronic structure changes accompanying the non-adiabatic transition of an excited molecule from the singlet to the triplet manifold. Core-level X-ray spectroscopy at the carbon-1s K-edge (284 eV) is applied to identify the role of the triplet state (T1, 3ππ*) in the ultraviolet-induced photochemistry of pentane-2,4-dione (acetylacetone, AcAc). The excited-state dynamics initiated at 266 nm (1ππ*, S2) is investigated with element- and site-specificity using broadband soft X-ray pulses produced by high harmonic generation, in combination with time-dependent density functional theory calculations of the X-ray spectra for the excited electronic singlet and triplet states. The evolution of the core-to-valence resonances at the carbon K-edge establishes an ultrafast population of the T1 state (3ππ*) in AcAc via intersystem crossing on a 1.5 ± 0.2 ps time scale.

Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction.

The ultrafast light-activated electrocyclic ring-opening reaction of 1,3-cyclohexadiene is a fundamental prototype of photochemical pericyclic reactions. Generally, these reactions are thought to proceed through an intermediate excited-state minimum (the so-called pericyclic minimum), which leads to isomerization via nonadiabatic relaxation to the ground state of the photoproduct. Here, we used femtosecond (fs) soft x-ray spectroscopy near the carbon K-edge (~284 electron volts) on a tabletop apparatus to directly reveal the valence electronic structure of this transient intermediate state. The core-to-valence spectroscopic signature of the pericyclic minimum observed in the experiment was characterized, in combination with time-dependent density functional theory calculations, to reveal overlap and mixing of the frontier valence orbital energy levels. We show that this transient valence electronic structure arises within 60 ± 20 fs after ultraviolet photoexcitation and decays with a time constant of 110 ± 60 fs.

Identification of absolute geometries of cis and trans molecular isomers by Coulomb Explosion Imaging.

An experimental route to identify and separate geometric isomers by means of coincident Coulomb explosion imaging is presented, allowing isomer-resolved photoionization studies on isomerically mixed samples. We demonstrate the technique on cis/trans 1,2-dibromoethene (C2H2Br2). The momentum correlation between the bromine ions in a three-body fragmentation process induced by bromine 3d inner-shell photoionization is used to identify the cis and trans structures of the isomers. The experimentally determined momentum correlations and the isomer-resolved fragment-ion kinetic energies are matched closely by a classical Coulomb explosion model.

Multiple Ionization of Free Ubiquitin Molecular Ions in Extreme Ultraviolet Free-Electron Laser Pulses.

The fragmentation of free tenfold protonated ubiquitin in intense 70 femtosecond pulses of 90 eV photons from the FLASH facility was investigated. Mass spectrometric investigation of the fragment cations produced after removal of many electrons revealed fragmentation predominantly into immonium ions and related ions, with yields increasing linearly with intensity. Ionization clearly triggers a localized molecular response that occurs before the excitation energy equilibrates. Consistent with this interpretation, the effect is almost unaffected by the charge state, as fragmentation of sixfold deprotonated ubiquitin leads to a very similar fragmentation pattern. Ubiquitin responds to EUV multiphoton ionization as an ensemble of small peptides.