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Physical chemistry, chemical physics 24, 28825 - 28830 (2022). doi:10.1039/D2CP03411E special issue: "Ions, electrons, coincidences and dynamics: Festschrift for John H.D. Eland", Symmetry breaking and competition between electronic decay and nuclear dynamics are major factors determining whether the memory of the initial core-hole localisation in a molecule is retained long enough to affect fragmentation. We investigate the fate of core holes localised at different sites in the free 1,3 trans butadiene molecule by using synchrotron radiation to selectively excite core electrons from different C 1s sites to the π∗ orbital (LUMO). Fragmentation involving bonds localised at the site of the core hole provides clear evidence for preferential bond breaking for a core hole located at the terminal carbon site, while the signature of localisation is weak for a vacancy on the central carbon site. The origin of this difference is attributed to out-of-plane vibrations, and statistical evaporation of protons for central carbon vacancies., Published by RSC Publ., Cambridge

Review of scientific instruments 93(11), 115111 (2022). doi:10.1063/5.0097525, The development and characterization of an angle-resolved photoelectron spectrometer, based on the electron time-of-flight concept, for hard x-ray photon diagnostics at the European Free-Electron Laser, are described. The instrument is meant to provide users and operators with pulse-resolved, non-invasive spectral distribution diagnostics, which in the hard x-ray regime is a challenge due to the poor cross-section and high kinetic energy of photoelectrons for the available target gases. We report on the performances of this instrument as obtained using hard x-rays at the PETRA III synchrotron at DESY in multibunch mode. Results are compared with electron trajectory simulations. We demonstrate a resolving power of 10 eV at incident photon energies up to at least 20 keV., Published by American Institute of Physics, [S.l.]

Communications Physics 5(1), 191 (2022). doi:10.1038/s42005-022-00962-8, High-intensity ultrashort X-ray free-electron laser (XFEL) pulses are revolutionizing the study of fundamental nonlinear x-ray matter interactions and coupled electronic and nuclear dynamics. To fully exploit the potential of this powerful tool for advanced x-ray spectroscopies, a noninvasive spectral characterization of incident stochastic XFEL pulses with high resolution is a key requirement. Here we present a methodology that combines high-acceptance angle-resolved photoelectron time-of-flight spectroscopy and ghost imaging to enhance the quality of spectral characterization of x-ray free-electron laser pulses. Implementation of this noninvasive high-resolution x-ray diagnostic can greatly benefit the ultrafast x-ray spectroscopy community by functioning as a transparent beamsplitter for applications such as transient absorption spectroscopy in averaging mode as well as covariance-based x-ray nonlinear spectroscopies in single-shot mode where the shot-to-shot fluctuations inherent to a self-amplified spontaneous emission (SASE) XFEL pulse are a powerful asset., Published by Springer Nature, London

Harmonic lasing provides an opportunity to extend the photon energy range of existing and planned x-ray free electron laser (FEL) user facilities. Contrary to nonlinear harmonic generation, harmonic lasing can generate a much more intense, stable, and narrow-band FEL beam. Another interesting application is harmonic lasing self-seeding that allows to improve the longitudinal coherence and spectral power of a self-amplified spontaneous emission FEL. This concept was tested at the soft x-ray FEL user facility FLASH in the range of 4.5–15 nm and at Pohang accelerator laboratory X-ray Free Electron Laser (XFEL) at 1 nm. In this paper we present recent results from the European XFEL where we successfully demonstrated harmonic lasing at 5.9 Angstrom and 2.8 Angstrom. In the latter case we obtained both third and fifth harmonic lasing and, for the first time, operated a harmonic lasing cascade (fifth-third-first harmonics of the undulator). These results pave the way for reaching very high photon energies, up to 100 keV.

In this paper, we examine decay and fragmentation of core-excited and core-ionized water molecules combining quantum chemical calculations and electron-energy-resolved electron-ion coincidence spectroscopy. The experimental technique allows us to connect electronic decay from core-excited states, electronic transitions between ionic states, and dissociation of the molecular ion. To this end, we calculate the minimum energy dissociation path of the core-excited molecule and the potential energy surfaces of the molecular ion. Our measurements highlight the role of ultra-fast nuclear motion in the 1a

In this paper, we examine decay and fragmentation of core-excited and core-ionized water molecules combining quantum chemical calculations and electron-energy-resolved electron–ion coincidence spectroscopy. The experimental technique allows us to connect electronic decay from core-excited states, electronic transitions between ionic states, and dissociation of the molecular ion. To this end, we calculate the minimum energy dissociation path of the core-excited molecule and the potential energy surfaces of the molecular ion. Our measurements highlight the role of ultra-fast nuclear motion in the 1a1−14a1" role="presentation" style="display: inline; line-height: normal; word-spacing: normal; overflow-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; position: relative;">1a−114a11a1−14a1 core-excited molecule in the production of fragment ions. OH+ fragments dominate for spectator Auger decay. Complete atomization after sequential fragmentation is also evident through detection of slow H+ fragments. Additional measurements of the non-resonant Auger decay of the core-ionized molecule (1a1−1" role="presentation" style="display: inline; line-height: normal; word-spacing: normal; overflow-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; position: relative;">1a−111a1−1) to the lower-energy dication states show that the formation of the OH+ + H+ ion pair dominates, whereas sequential fragmentation OH+ + H+ → O + H+ + H+ is observed for transitions to higher dication states, supporting previous theoretical investigations.

Applied Sciences 10(8), 2728 (2020). doi:10.3390/app10082728, X-ray pump/X-ray probe applications are made possible at X-ray Free Electron Laser (XFEL) facilities by generating two X-ray pulses with different wavelengths and controllable temporal delay. In order to enable this capability at the European XFEL, an upgrade project to equip the soft X-ray SASE3 beamline with a magnetic chicane is underway. In the present paper we describe the status of the project, its scientific focus and expected performance, including start-to-end simulations of the photon beam transport up to the sample, as well as recent experimental results demonstrating two-color lasing at photon energies of 805 eV + 835 eV and 910 eV + 950 eV. Additionally, we discuss methods to analyze the spectral properties and the intensity of the generated radiation to provide on-line diagnostics for future user experiments., Published by MDPI, Basel

Journal of synchrotron radiation 26(4), 1045 - 1051 (2019). doi:10.1107/S1600577519003795, X-ray gas monitors (XGMs) are operated at the European XFEL for non-invasive single-shot pulse energy measurements and average beam position monitoring. They are used for tuning and maintaining the self-amplified spontaneous emission (SASE) operation and for sorting single-shot experimental data according to the pulse-resolved energy monitor data. The XGMs were developed at DESY based on the specific requirements for the European XFEL. In total, six XGM units are continuously in operation. Here, the main principle and experimental setup of an XGM are summarized, and the locations of the six XGMs at the facility are shown. Pulse energy measurements at 0.134 nm wavelength are presented, exceeding 1 mJ obtained with an absolute measurement uncertainty of 7–10%; correlations between different XGMs are shown, from which a SASE1 beamline transmission of 97% is deduced. Additionally, simultaneous position measurements close to the undulator and at the end of the tunnel are shown, along with the correlation of beam position data simultaneously acquired by an XGM and an imager., Published by Wiley-Blackwell, [S.l.]

Commissioning and first operation of an angle-resolved photoelectron spectrometer for non-invasive shot-to-shot diagnostics at the European XFEL soft X-ray beamline are described. The objective with the instrument is to provide the users and operators with reliable pulse-resolved information regarding photon energy and polarization that opens up a variety of applications for novel experiments but also hardware optimization.

The European X-ray Free Electron Laser (European XFEL) is a new user facility in the metropolitan area of Hamburg, Germany. It offers ultra-short (femtosecond) and intense (GigaWatt) transversely coherent x-ray laser beams in the soft to hard x-ray domain at MHz repetition rate. Up to 2700 pulses per train will be delivered at 10 Hz train repetition rate. The x-ray diagnostics [1-4] serves the electron machine to achieve lasing by Self-Amplified Spontaneous Emission (SASE), supports the SASE tuning, and assists to align and commission the photon beam transport. Finally, it delivers non-invasive online beam diagnostic data to the users at the experimental end-stations. In May 2017 the first undulator beamline, SASE1, was successfully commissioned with beam, and First Lasing was detected. This presentation describes the contribution of photon diagnostics during the distinct commissioning phases: Pre-beam checkout, first light from the bending magnets, x-rays from single undulator segments, SASE tuning with many undulator segments, First Lasing, optics alignment for FEL beam transport through the tunnel up to the experimental hutches, and finally beam delivery to first users. Assessed beam properties included per-pulse intensity, beam position, shape, lateral dimensions, and spectral properties. During this period, the machine provided up to 0.1 nm wavelength at up to 1.5 mJ pulse energy, up to 300 FEL pulses per train, and up to 4.5 MHz intra-bunch train repetition.The European X-ray Free Electron Laser (European XFEL) is a new user facility in the metropolitan area of Hamburg, Germany. It offers ultra-short (femtosecond) and intense (GigaWatt) transversely coherent x-ray laser beams in the soft to hard x-ray domain at MHz repetition rate. Up to 2700 pulses per train will be delivered at 10 Hz train repetition rate. The x-ray diagnostics [1-4] serves the electron machine to achieve lasing by Self-Amplified Spontaneous Emission (SASE), supports the SASE tuning, and assists to align and commission the photon beam transport. Finally, it delivers non-invasive online beam diagnostic data to the users at the experimental end-stations. In May 2017 the first undulator beamline, SASE1, was successfully commissioned with beam, and First Lasing was detected. This presentation describes the contribution of photon diagnostics during the distinct commissioning phases: Pre-beam checkout, first light from the bending magnets, x-rays from single undulator segments, SASE tuning with ...

Review of scientific instruments 91(10), 103101 (2020). doi:10.1063/5.0019935, The European X-ray Free-Electron Laser Facility in Germany delivers x-ray pulses with femtosecond pulse duration at a repetition rate of up to 4.5 MHz. The free-electron laser radiation is created by the self-amplified spontaneous emission (SASE) process, whose stochastic nature gives rise to shot-to-shot fluctuations in most beam properties, including spectrum, pulse energy, spatial profile, wavefront, and temporal profile. Each spectrum consisting of many spikes varies in width and amplitude that appear differently within the envelope of the SASE spectrum. In order to measure and study the SASE spectrum, the HIgh REsolution hard X-ray single-shot (HIREX) spectrometer was installed in the photon tunnel of the SASE1 undulator beamline. It is based on diamond gratings, bent crystals as a dispersive element, and a MHz-repetition-rate strip detector. It covers a photon energy range of 3 keV–25 keV and a bandwidth of 0.5% of the SASE beam. The SASE spikes are resolved with 0.15 eV separation using the Si 440 reflection, providing a resolving power of 60 000 at a photon energy of 9.3 keV. The measured SASE bandwidth is 25 eV. In this paper, we discuss the design specifications, installation, and commissioning of the HIREX spectrometer. The spectral results using Si (110), Si (111), and C (110) crystals are presented., Published by American Institute of Physics, [S.l.]

Journal of synchrotron radiation 26(5), 1422 - 1431 (2019). doi:10.1107/S1600577519006611, Published by Wiley-Blackwell, [S.l.]

The chemical bond scission of methylbenzoate (C6H5CO2CH3) following core excitation at the C and O K edges was examined from partial ion yield measurements across these edges using synchrotron radiation. Site-specific scission of the C-O bonds was observed at both edges. Theoretical X-ray absorption spectra (XAS) were obtained using density functional theory. Peak assignments in the observed spectra were found to be consistent with the theory. From core-excited state dynamics calculations, an elongation of the C-O bond was predicted and provides an explanation of the observed partial ion yield enhancement of CH3+ and C6H5CO+ at the core-excited resonances at both edges.

The development of a high precision five rotation axes polarimeter using transmission multilayers as polarizers and reflection multilayers as analyzers is presented. In order to cover a wide energy range from EUV to soft X-ray, a set of Mo/Si, Cr/C, Sc/Cr, and W/B4C multilayers for transmission and reflection have been designed and fabricated. A hexapod support allows to align the polarimeter easily relative to the optical axis, and the instrument is designed to be moved conveniently between different beamlines.

Nuclear motion in the N1s(-1)4a core-excited state of ammonia is investigated by studying the angular anisotropy of fragments produced in the decay of the highly excited molecule and compared with predictions from ab initio calculations. Two different fragmentation channels (H(+)/NH2(+) and H(+)/NH(+)/H) reveal complex nuclear dynamics as the excitation photon energy is tuned through the 4a1 resonance. The well-defined angular anisotropy of the fragments produced in the dissociation of the molecular dication species suggests a very rapid nuclear motion and the time scale of the nuclear dynamics is limited to the low fs timescale.

Dissociative double photoionization of cyclopropane is studied in the inner-valence region using tunable synchrotron radiation. With the aid of ab initio quantum chemical calculations the energies of dication states and their favoured fragmentation pathways are determined. These are compared to the experimental appearance energies of two-body fragmentation processes and to the kinetic energy released upon dissociation. Photon energy dependent state-selective dissociation in the 25–35 eV range is found. Calculations of dissociation pathways suggest that cyclopropane ring-deformation is selectively triggered at certain photon energies. The calculations suggest that initial ring deformation essentially determines the population of different dication states that function as gateways for particular dissociation channels. The measurements show that stepwise ionization processes populate dissociative 3e′−2 states via ring-opening and Jahn–Teller active states at photon energies below the double-ionization threshold. For energies above the double-ionization threshold the kinematics indicate that double ionization takes place predominantly within the Franck–Condon region populating 3e′−1 1e′′−1 states.

The charge and proton dynamics in hydrogen-bonded networks are investigated using ammonia as a model system. The fragmentation dynamics of medium-sized clusters (1-2 nm) upon single photon multi-ionization is studied, by analyzing the momenta of small ionic fragments. The observed fragmentation pattern of the doubly- and triply- charged clusters reveals a spatial anisotropy of emission between fragments (back-to-back). Protonated fragments exhibit a distinct kinematic correlation, indicating a delay between ionization and fragmentation (fission). The different kinematics observed for channels containing protonated and unprotonated species provides possible insights into the prime mechanisms of charge and proton transfer, as well as proton hopping, in such a nanoscale system., Comment: 9 pages, 6 figures

Photofragmentation of gas-phase acetamide and acetic acid clusters produced by a supersonic expansion source has been studied using time-of-flight mass spectrometry and the partial ion yield (PIY) technique combined with tunable vacuum-ultraviolet synchrotron radiation. Appearance energies of the clusters and their fragments were experimentally determined from the PIY measurements. The effect of clusterization conditions on the formation and fragmentation of acetic acid clusters was investigated. Ab initio quantum mechanical calculations were performed on both samples' dimers to find their neutral and ionized geometries as well as proton transfer energy barriers leading to the optimal geometries. In the case of the acetamide dimer, the reaction resulting in the production of ammoniated acetamide was probed, and the geometry of the obtained ion was calculated.

A photoelectron-ion-ion coincidence experiment has been carried out on the amino acid molecule cysteine after core-ionization of the O 1s, N 1s, C 1s, and S 2p orbitals. A number of different dissociation channels have been identified. Some of them show strong site-selective dependence that can be attributed to a combination of nuclear motion in the core-ionized state and Auger processes that populate different final electronic states in the dication.

Dissociative double-photoionization of butadiene in the 25-45 eV energy range has been studied with tunable synchrotron radiation using full three-dimensional ion momentum imaging. Using ab initio calculations, the electronic states of the molecular dication below 33 eV are identified. The results of the measurement and calculation show that double ionization from π orbitals selectively triggers twisting about the terminal or central C–C bonds. We show that this conformational rearrangement depends upon the dication electronic state, which effectively acts as a gateway for the dissociation reaction pathway. For photon energies above 33 eV, three-body dissociation channels where neutral H-atom evaporation precedes C–C charge-separation in the dication species appear in the correlation map. The fragment angular distributions support a model where the dication species is initially aligned with the molecular backbone parallel to the polarization vector of the light, indicating a high probability for double-ionization to the “gateway states” for molecules with this orientation.

International audience; This combined experimental and theoretical study demonstrates that the surface plasmon resonance in C60 alters the valence photoemission quantum phase, resulting in strong effects in the photoelectron angular distribution and emission time delay. Electron momentum imaging spectroscopy is used to measure the photoelectron angular distribution asymmetry parameter that agrees well with our calculations from the time-dependent local density approximation (TDLDA). Significant structure in the valence photoemission time delay is simultaneously calculated by TDLDA over the plasmon active energies. Results reveal a unified spatial and temporal asymmetry pattern driven by the plasmon resonance and offer a sensitive probe of electron correlation. A semiclassical approach facilitates further insights into this link that can be generalized and applied to other molecular systems and nanometer-sized metallic materials exhibiting plasmon resonances.

International audience; We perform time-dependent local density functional calculations of the time delay in C60 HOMO and HOMO-1 photoionization at giant plasmon energies. A semiclassical model is used to develop further insights.

A high precision five rotation-axes polarimeter using transmission multilayers as polarizers and reflection multilayers as analyzers has been designed and manufactured. To cover the extreme ultraviolet regime, Mo/Si, Cr/C, Sc/Cr, and W/B4C multilayers for transmission and reflection have also been designed and produced. The polarimeter mechanics is supported on a hexapod to simplify the alignment relative to photon beam. The instrument is designed so that it can be easily transferred between different beamlines.

The fragmentation of the doubly-charged carbon dioxide molecule is studied after photoexcitation to the C 1s(1)2π(u) and O 1s(1)2π(u) states using a multicoincidence ion-imaging technique. The bent component of the Renner-Teller split states populated in the 1s→ π∗ resonant excitation at both the carbon and oxygen 1s ionization edges opens pathways to potential surfaces in highly bent geometries in the dication. Evidence for a complete deformation of the molecule is found in the coincident detection of C(+) and O(2) (+) ions. The distinct alignment of this fragmentation channel indicates rapid deformation and subsequent fragmentation. Investigation of the complete atomization dynamics in the dication leading to asymmetric charge separation shows that the primary dissociation mechanisms, sequential, concerted, and asynchronous concerted, are correlated to specific fragment kinetic energies. The study shows that the bond angle in fragmentation can extend below 20°.

The electronic structure and photofragmentation in outer and inner valence regions of Se-n (n

The angular anisotropy for selected dissociation channels is measured at resonantly excited states of Σ and Π symmetries at the C and O K-shell ionization edges of carbonyl sulfide. While the kinetic energy released in the reaction is mainly independent of the excitation energy, the angular anisotropy and momentum correlation clearly show deformation of the OCS molecule in the C 1s(-1)π(∗1) state. The discovery of a two-body fragmentation channel SO(+)/C(+) with a well defined angular anisotropy indicates the rapid formation of the CSO isomeric species.

The study focuses on rapid nuclear rearrangement/isomerization taking place in an early stage of butadiene fragmentation using multiple ion momentum imaging spectroscopy and tunable synchrotron radiation. In addition, ab initio calculations are performed to disentangle the nuclear dynamics preceding dissociation.

Experimental studies of core-excited molecules using three-dimensional multi particle momentum imaging are presented where bond rearrangement processes in dication species are analysed. The aim of the study is to understand the relation between the geometric changes associated with core-excited states and the kinetic energy released in particular molecular dissociation processes. The kinematics of individual fragmentation channels are studied by fully three-dimensional momentum imaging of fragments in coincidence. Examples are presented where the high efficiency of the instrument and the fully three-dimensional momentum capabilities are exploited to understand nuclear motion leading to bond rearrangement in core-excited states. We identify bond-rearrangement processes in water, carbonyl sulphide and acetylene which are initiated in the core-excited state. In water this is evidenced by the H-2(+)/O+ ion pair, and in carbonyl sulphide the OS++C+ pair is the fingerprint of this reaction. In acetylene the H-2(+) + C-2(+) ion pair indicates a molecular geometry that changes from linear to strongly bent. We measure the angular distribution of all fragments and fragment pairs and for the bond rearrangement processes in water and in core-excited acetylene the angular distribution of fragments suggests that the bond rearrangement is very rapid. (Less)

The angular anisotropy of fragments created in the dissociation of core-electron excited water molecules is studied to probe the correlation between fragmentation channels, kinematics and molecular geometry. We present fragment kinetic measurements for water molecules where the inner-shell oxygen electron is excited to the unoccupied 4a1 and 2b2 valence molecular orbitals. The kinematics of individual fragmentation channels are measured using fully three-dimensional momentum imaging of fragments. The results show that the geometry of the molecule and the kinetic energy of fragments are strongly coupled in the atomisation process. In addition we identify a fragmentation process arising from bond rearrangement evidenced by the H2(+)-O(+) ion pair which is accessible for resonant excitation of the 1s electron. In all of the two-body fragmentation processes the dissociation takes place along the potential-energy surface, while atomisation reveals both dissociation along the potential surface and Coulomb explosion. The angular distribution of fragments suggests that the bond rearrangement is very rapid; likely on a sub 10 fs time scale.

Ab initio and mass-resolved fragmentation study of thermally evaporated selenium clusters Sen induced by VUV synchrotron radiation.

The photo-fragmentation of ammonia molecular clusters ionized with soft x-rays is studied for photon energies near the N-1s threshold. The fragmentation is studied with a 3D momentum mass spectrometer to access the energy and angular correlations between fragments. By choosing the cluster sizes below or above the critical size of stable dication, we investigate the coulomb explosion dynamics and the interplay between charge delocalization and mobility of molecules in the clusters.

The study focuses on the rapid geometry change in ethyne excited near the carbon 1s edge. Core excitation and ionization lead to population of dicationic states in ethyne. We study three competing dissociation pathways associated with deprotonation in the linear ethyne molecule, and two cases of rapid proton migration. We investigate the alignment of the molecule in the excited state and find startling differences in these three cases. We present evidence for a strong anisotropy in the production of H(2)(+)/C(2)(+) fragments through a rapid deformation of the molecule to a dibridged conformation with the transition dipole moment parallel to the polarization of the exciting radiation.