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Accurate computations of experimental observables are essential for interpreting the high information content held within x-ray spectra. However, for complicated systems this can be difficult, a challenge compounded when dynamics becomes important owing to the large number of calculations required to capture the time-evolving observable. While machine learning architectures have been shown to represent a promising approach for rapidly predicting spectral lineshapes, achieving simultaneously accurate and sufficiently comprehensive training data is challenging. Herein, we introduce Δ-learning for x-ray spectroscopy. Instead of directly learning the structure-spectrum relationship, the Δ-model learns the structure dependent difference between a higher and lower level of theory. Consequently, once developed these models can be used to translate spectral shapes obtained from lower levels of theory to mimic those corresponding to higher levels of theory. Ultimately, this achieves accurate simulations with a much reduced computational burden as only the lower level of theory is computed, while the model can instantaneously transform this to a spectrum equivalent to a higher level of theory. Our present model, demonstrated herein, learns the difference between TDDFT(BLYP) and TDDFT(B3LYP) spectra. Its effectiveness is illustrated using simulations of Rh L3-edge spectra tracking the C–H activation of octane by a cyclopentadienyl rhodium carbonyl complex. [ABSTRACT FROM AUTHOR]

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Seemingly simple yet surprisingly difficult to probe, excess protons in water constitute complex quantum objects with strong interactions with the extended and dynamically changing hydrogen‐bonding network of the liquid. Proton hydration plays pivotal roles in energy transport in hydrogen fuel cells and signal transduction in transmembrane proteins. While geometries and stoichiometry have been widely addressed in both experiment and theory, the electronic structure of these specific hydrated proton complexes has remained elusive. Here we show, layer by layer, how utilizing novel flatjet technology for accurate x‐ray spectroscopic measurements and combining infrared spectral analysis and calculations, we find orbital‐specific markers that distinguish two main electronic‐structure effects: Local orbital interactions determine covalent bonding between the proton and neigbouring water molecules, while orbital‐energy shifts measure the strength of the extended electric field of the proton. [ABSTRACT FROM AUTHOR]

Photoacids show a strong increase in acidity in the first electronic excited state, enabling real‐time studies of proton transfer in acid‐base reactions, proton transport in energy storage devices and biomolecular sensor protein systems. Several explanations have been proposed for what determines photoacidity, ranging from variations in solvation free energy to changes in electronic structure occurring along the four stages of the Förster cycle. Here we use picosecond nitrogen K‐edge spectroscopy to monitor the electronic structure changes of the proton donating group in a protonated aromatic amine photoacid in solution upon photoexcitation and subsequent proton transfer dynamics. Probing core‐to‐valence transitions locally at the amine functional group and with orbital specificity, we clearly reveal pronounced electronic structure, dipole moment and energetic changes on the conjugate photobase side. This result paves the way for a detailed electronic structural characterization of the photoacidity phenomenon. [ABSTRACT FROM AUTHOR]

Copyright of Angewandte Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Early excited state dynamics in the photodissociation of transition metal carbonyls determines the chemical nature of short-lived catalytically active reaction intermediates. However, time-resolved experiments have not yet revealed mechanistic details in the sub-picosecond regime. Hence, in this study the photoexcitation of ironpentacarbonyl Fe(CO)5 is simulated with semi-classical excited state molecular dynamics. We find that the bright metal-to-ligand charge-transfer (MLCT) transition induces synchronous Fe-C oscillations in the trigonal bipyramidal complex leading to periodically reoccurring release of predominantly axial CO. Metaphorically the photoactivated Fe(CO)5 acts as a CO geyser, as a result of dynamics in the potential energy landscape of the axial Fe-C distances and non-adiabatic transitions between manifolds of bound MLCT and dissociative metal-centered (MC) excited states. The predominant release of axial CO ligands and delayed release of equatorial CO ligands are explained in a unified mechanism based on the σ*(Fe-C) anti-bonding character of the receiving orbital in the dissociative MC states. The photodissociation of transition metal carbonyls is involved in catalysis and synthetic processes. Here the authors, using semi-classical excited state molecular dynamics, observe details of the early stage dynamics in the photodissociation of Fe(CO)5, including synchronous bursts of CO at periodic intervals of 90 femtoseconds. [ABSTRACT FROM AUTHOR]

The atomic specificity of X-ray spectroscopies provides a distinct perspective on molecular electronic structure. For 3d metal coordination and organometallic complexes, the combination of metal- and ligand-specific X-ray spectroscopies directly interrogates metal–ligand covalency—the hybridization of metal and ligand electronic states. Resonant inelastic X-ray scattering (RIXS), the X-ray analog of resonance Raman scattering, provides access to all classes of valence excited states in transition-metal complexes, making it a particularly powerful means of characterizing the valence electronic structure of 3d metal complexes. Recent advances in X-ray free-electron laser sources have enabled RIXS to be extended to the ultrafast time domain. We review RIXS studies of two archetypical photochemical processes: charge-transfer excitation in ferricyanide and ligand photodissociation in iron pentacarbonyl. These studies demonstratefemtosecond-resolution RIXS can directly characterize the time-evolving electronic structure, including the evolution of the metal–ligand covalency. [ABSTRACT FROM AUTHOR]

The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water. [ABSTRACT FROM AUTHOR]

Hard X-ray spectroscopy is an element specific probe of electronic state, but signals are weak and require intense light to study low concentration samples. Free electron laser facilities offer the highest intensity X-rays of any available light source. The light produced at such facilities is stochastic, with spikey, broadband spectra that change drastically from shot to shot. Here, using aqueous ferrocyanide, we show that the resonant X-ray emission (RXES) spectrum can be inferred by correlating for each shot the fluorescence intensity from the sample with spectra of the fluctuating, self-amplified spontaneous emission (SASE) source. We obtain resolved narrow and chemically rich information in core-to-valence transitions of the pre-edge region at the Fe K-edge. Our approach avoids monochromatization, provides higher photon flux to the sample, and allows non-resonant signals like elastic scattering to be simultaneously recorded. The spectra obtained match well with spectra measured using a monochromator. We also show that inaccurate measurements of the stochastic light spectra reduce the measurement efficiency of our approach. X-ray absorption and X-ray free electron lasers are important tools to study chemical and structural dynamics, but spectral details like pre-edge features are inherently hard to detect. Here, the authors show that stochastic spectroscopy can yield similar spectral information to monochromatic spectroscopies, while increasing signal yield and reducing acquisition time. [ABSTRACT FROM AUTHOR]

We report the nearest-neighbor oxygen-oxygen radial distribution function (NN O–O RDF) of room temperature liquid water and polycrystalline ice Ih (-16.8 °C) obtained by x-ray Raman based extended x-ray absorption fine structure (EXAFS) spectroscopy. The spectra of the two systems were taken under identical experimental conditions using the same procedures to obtain the NN O–O RDFs. This protocol ensured a measurement of the relative distance distribution with very small systematic errors. The NN O–O RDF of water is found to be more asymmetric (tail extending to longer distances) with longer average distance (2.81 Å for water and 2.76 Å for ice) but a slightly shorter peak position (2.70 Å for water and 2.71 Å for ice). The refinement also showed a small but significant contribution from the linear O–H–O multiple scattering signal. The high sensitivity to short range distances of the EXAFS probe will set further restrictions to the range of possible models of liquid water. [ABSTRACT FROM AUTHOR]

We present a combined x-ray absorption spectroscopy/computational study of water in hydrochloric acid (HCl) solutions of varying concentration to address the structure and bonding of excess protons and their effect on the hydrogen bonding network in liquid water. Intensity variations and energy shifts indicate changes in the hydrogen bonding structure in water as well as the local structure of the protonated complex as a function of the concentration of protons. In particular, in highly acidic solutions we find a dominance of the Eigen form, H3O+, while the proton is less localized to a specific water under less acidic conditions. [ABSTRACT FROM AUTHOR]

X-ray free-electron lasers with intense, tuneable and short-pulse X-ray radiation are transformative tools for the investigation of transition-metal complexes and metalloproteins. This becomes apparent in particular when combining the experimental observables from X-ray spectroscopy with modern theoretical tools for calculations of electronic structures and X-ray spectra from first principles. The combination gives new insights into how charge and spin densities change in chemical reactions and how they determine reactivity. This is demonstrated for the investigations of structural dynamics with metal K-edge absorption spectroscopy, spin states in excited-state dynamics with metal 3p-3d exchange interactions, the frontier-orbital interactions in dissociation and substitution reactions with metalspecific X-ray spectroscopy, and studies of metal oxidation states with femtosecond pulses for 'probebefore-destroy' spectroscopy. The role of X-ray free-electron lasers is addressed with thoughts about how they enable 'bringing back together' different aspects of the same problem and this is thought to go beyond a conventional review paper where these aspects are formulated in italic font type in a prequel, an interlude and in a sequel. [ABSTRACT FROM AUTHOR]

X-ray induced sample damage can impede electronic and structural investigations of radiation-sensitive samples studied with X-rays. Here we quantify dose-dependent sample damage to the prototypical MnIII(acac)3 complex in solution and at room temperature for the soft X-ray range, using X-ray absorption spectroscopy at the Mn L-edge. We observe the appearance of a reduced MnII species as the X-ray dose is increased. We find a half-damage dose of 1.6 MGy and quantify a spectroscopically tolerable dose on the order of 0.3 MGy (1 Gy = 1 J kg−1), where 90% of MnIII(acac)3 are intact. Our dose-limit is around one order of magnitude lower than the Henderson limit (half-damage dose of 20 MGy) which is commonly employed for protein crystallography with hard X-rays. It is comparable, however, to the dose-limits obtained for collecting un-damaged Mn K-edge spectra of the photosystem II protein, using hard X-rays. The dose-dependent reduction of MnIII observed here for solution samples occurs at a dose limit that is two to four orders of magnitude smaller than the dose limits previously reported for soft X-ray spectroscopy of iron samples in the solid phase. We compare our measured to calculated spectra from ab initio restricted active space (RAS) theory and discuss possible mechanisms for the observed dose-dependent damage of MnIII(acac)3 in solution. On the basis of our results, we assess the influence of sample damage in other experimental studies with soft X-rays from storage-ring synchrotron radiation sources and X-ray free-electron lasers. [ABSTRACT FROM AUTHOR]

We describe how inversion symmetry separation of electronic state manifolds in resonant inelastic soft X-ray scattering (RIXS) can be applied to probe excited-state dynamics with compelling selectivity. In a case study of Fe L3-edge RIXS in the ferricyanide complex Fe(CN)63−, we demonstrate with multi-configurational restricted active space spectrum simulations how the information content of RIXS spectral fingerprints can be used to unambiguously separate species of different electronic configurations, spin multiplicities, and structures, with possible involvement in the decay dynamics of photo-excited ligand-to-metal charge-transfer. Specifically, we propose that this could be applied to confirm or reject the presence of a hitherto elusive transient Quartet species. Thus, RIXS offers a particular possibility to settle a recent controversy regarding the decay pathway, and we expect the technique to be similarly applicable in other model systems of photo-induced dynamics. [ABSTRACT FROM AUTHOR]

We present a setup combining a liquid flatjet sample delivery and a MHz laser system for time-resolved soft X-ray absorption measurements of liquid samples at the high brilliance undulator beamline UE52-SGM at Bessy II yielding unprecedented statistics in this spectral range. We demonstrate that the efficient detection of transient absorption changes in transmission mode enables the identification of photoexcited species in dilute samples. With iron(II)-trisbipyridine in aqueous solution as a benchmark system, we present absorption measurements at various edges in the soft X-ray regime. In combination with the wavelength tunability of the laser system, the set-up opens up opportunities to study the photochemistry of many systems at low concentrations, relevant to materials sciences, chemistry, and biology. [ABSTRACT FROM AUTHOR]

Keywords: Eigen-Kation; Elektronische Struktur; Hydratisiertes Proton; Weiche Röntgenabsoprtionsspektroskopie; Zundel-Kation DE Eigen-Kation Elektronische Struktur Hydratisiertes Proton Weiche Röntgenabsoprtionsspektroskopie Zundel-Kation 1 1 1 11/09/22 20221114 NES 221114 B Wie weit b reicht der Einfluss eines Protons in Wasser? Es ergibt sich eine strukturelle Hierarchie, in der das Proton stark mit den drei nächsten Wassermolekülen interagiert und einen hybridisierten H SB 7 sb O SB 3 sb SP + sp -Kern formt, während die erste Hydrathülle durch das elektrische Feld der positiven Protonenladung beeinflusst wird. Röntgenspektroskopie enthüllt - Schicht für Schicht - die elektronische Struktur von Wassermolekülen bei Hydratation eines Protons. [Extracted from the article]

A general architectural hierarchy exists in which the proton strongly interacts with the three nearest water molecules to form a hybridized H SB 7 sb O SB 3 sb SP + sp core while the first hydration shell is affected by the electric field of the proton's positive charge. Eigen Cation, Electronic Structure, Hydrated Proton, Soft X-Ray Absorption Spectroscopy, Zundel Cation Keywords: Eigen Cation; Electronic Structure; Hydrated Proton; Soft X-Ray Absorption Spectroscopy; Zundel Cation EN Eigen Cation Electronic Structure Hydrated Proton Soft X-Ray Absorption Spectroscopy Zundel Cation 1 1 1 11/09/22 20221114 NES 221114 B How far b does the influence of a proton reach in water?. [Extracted from the article]

X-ray spectroscopy is a powerful tool to study the local charge distribution of chemical systems. Together with the liquid jet it becomes possible to probe chemical systems in their natural environment, the liquid phase. In this work, we present X-ray absorption (XA), X-ray emission (XE) and resonant inelastic X-ray scattering (RIXS) data of pure water and various salt solutions and show the possibilities these methods offer to elucidate the nature of ion-water interaction. [ABSTRACT FROM AUTHOR]

We present a liquid flatjet system for solution phase soft-x-ray spectroscopy. The flatjet set-up utilises the phenomenon of formation of stable liquid sheets upon collision of two identical laminar jets. Colliding the two single water jets, coming out of the nozzles with 50 μm orifices, under an impact angle of 48° leads to double sheet formation, of which the first sheet is 4.6 mm long and 1.0 mm wide. The liquid flatjet operates fully functional under vacuum conditions (<10-3 mbar), allowing soft-x-ray spectroscopy of aqueous solutions in transmission mode. We analyse the liquid water flatjet thickness under atmospheric pressure using interferomeric or mid-infrared transmission measurements and under vacuum conditions by measuring the absorbance of the O K-edge of water in transmission, and comparing our results with previously published data obtained with standing cells with Si3N4 membrane windows. The thickness of the first liquid sheet is found to vary between 1.4-3 μm, depending on the transverse and longitudinal position in the liquid sheet. We observe that the derived thickness is of similar magnitude under 1 bar and under vacuum conditions. A catcher unit facilitates the recycling of the solutions, allowing measurements on small sample volumes (~10 ml). We demonstrate the applicability of this approach by presenting measurements on the N K-edge of aqueous NH4+. Our results suggest the high potential of using liquid flatjets in steady-state and time-resolved studies in the soft-x-ray regime. [ABSTRACT FROM AUTHOR]

Sebastian Eckert et al. show in their Research Article (e202200709) how time-resolved nitrogen K-edge spectroscopy along the Förster cycle of a photoacid provides key insight into the electronic structural factors responsible for the photoacidity phenomenon. Keywords: Aromaticity; Electronic Structure; Orbital Interactions; Photoacids; Time-Resolved Soft x-Ray Spectroscopy EN Aromaticity Electronic Structure Orbital Interactions Photoacids Time-Resolved Soft x-Ray Spectroscopy 1 1 1 06/29/22 20220704 NES 220704 B Photoacids b have been understood, since the pioneering work of Theodor Förster more than seven decades ago, to show a pronounced increase in acidity when electronically excited, but the underlying microscopic mechanisms have remained elusive. Aromaticity, Electronic Structure, Orbital Interactions, Photoacids, Time-Resolved Soft x-Ray Spectroscopy. [Extracted from the article]

Sebastian Eckert et al. demonstrieren in ihrem Forschungsartikel (e202200709), wie Photoacidität durch Änderungen der elektronischen Struktur einer Photosäure entlang des Förster-Zyklus verursacht wird, die mit zeitaufgelöster Stickstoff-K-Kanten-Spektroskopie verfolgt werden können. Innentitelbild: Änderungen der elektronischen Struktur einer Amino-Photosäure entlang des Förster Zyklus (Angew. Keywords: Aromatizität; Elektronische Struktur; Orbitalwechselwirkung; Photosäuren; Zeitaufgelöste Weichröntgenspektroskopie DE Aromatizität Elektronische Struktur Orbitalwechselwirkung Photosäuren Zeitaufgelöste Weichröntgenspektroskopie 1 1 1 06/29/22 20220704 NES 220704 B Photosäuren b weisen einen starken Anstieg ihrer Säurestärke im elektronisch angeregten Zustand auf, wie von Theodor Förster vor bereits 7 Jahrzehnten gezeigt wurde. [Extracted from the article]

A novel sample holder is introduced which allows for temperature dependent soft x-ray absorption spectroscopy of liquids in transmission mode. The setup is based on sample cells with x-ray transmissive silicon nitride windows. A cooling circuit allows for temperature regulation of the sample liquid between -10 °C and +50 °C. The setup enables to record soft x-ray absorption spectra of liquids in transmission mode with a temperature resolution of 0.5 K and better. Reliability and reproducibility of the spectra are demonstrated by investigating the characteristic temperature-induced changes in the oxygen K-edge x-ray absorption spectrum of liquid water. These are compared to the corresponding changes in the oxygen K-edge spectra from x-ray Raman scattering. [ABSTRACT FROM AUTHOR]

In resonant inelastic soft x-ray scattering (RIXS) from molecular and liquid systems, the interplay of ground state structural and core-excited state dynamical contributions leads to complex spectral shapes that partially allow for ambiguous interpretations. In this work, we dissect these contributions in oxygen K-edge RIXS from liquid alcohols. We use the scattering into the electronic ground state as an accurate measure of nuclear dynamics in the intermediate core-excited state of the RIXS process. We determine the characteristic time in the core-excited state until nuclear dynamics give a measurable contribution to the RIXS spectral profiles to τdyn=1.2 ± 0.8 fs. By detuning the excitation energy below the absorption resonance we reduce the effective scattering time below τdyn, and hence suppress these dynamical contributions to a minimum. From the corresponding RIXS spectra of liquid methanol, we retrieve the "dynamic-free" density of states and find that it is described solely by the electronic states of the free methanol molecule. From this and from the comparison of normal and deuterated methanol, we conclude that the split peak structure found in the lone-pair emission region at non-resonant excitation originates from dynamics in the O-H bond in the core-excited state. We find no evidence that this split peak feature is a signature of distinct ground state structural complexes in liquid methanol. However, we demonstrate how changes in the hydrogen bond coordination within the series of linear alcohols from methanol to hexanol affect the split peak structure in the liquid alcohols. [ABSTRACT FROM AUTHOR]

A novel sample holder for soft x-ray absorption spectroscopy of liquids in transmission mode based on sample cells with x-ray transparent silicon nitride membranes is introduced. The sample holder allows for a reliable preparation of ultrathin liquid films with an adjustable thickness in the nm-μm range. This enables measurements of high quality x-ray absorption spectra of liquids in transmission mode, as will be shown for the example of liquid H2O, aqueous solutions of 3d-transition metal ions and alcohol-water mixtures. The fine structure of the x-ray absorption spectra is not affected by the sample thickness. No effects of the silicon nitride membranes were observed in the spectra. It is shown how an inhomogeneous thickness of the sample affects the spectra and how this can be avoided. [ABSTRACT FROM AUTHOR]

A laser-based tabletop approach to femtosecond time-resolved photoelectron spectroscopy with photons in the vacuum-ultraviolet (VUV) energy range is described. The femtosecond VUV pulses are produced by high-order harmonic generation (HHG) of an amplified femtosecond Ti:sapphire laser system. Two generations of the same setup and results from photoelectron spectroscopy in the gas phase are discussed. In both generations, a toroidal grating monochromator was used to select one harmonic in the photon energy range of 20-30 eV. The first generation of the setup was used to perform photoelectron spectroscopy in the gas phase to determine the bandwidth of the source. We find that our HHG source has a bandwidth of 140 ± 40 meV. The second and current generation is optimized for femtosecond pump-probe photoelectron spectroscopy with high flux and a small spot size at the sample of the femtosecond probe pulses. The VUV radiation is focused into the interaction region with a toroidal mirror to a spot smaller than 100 × 100 μm2 and the flux amounts to 1010 photons/s at the sample at a repetition rate of 1 kHz. The duration of the monochromatized VUV pulses is determined to be 120 fs resulting in an overall pump-probe time resolution of 135 ± 5 fs. We show how this setup can be used to map the transient valence electronic structure in molecular dissociation. [ABSTRACT FROM AUTHOR]

This article reports that more than 90 participants from Europe, the U.S. and Japan gathered from April 27 to 29, 2005, in Berlin, Germany, to hold a lively international meeting on time-resolved soft X-ray science. The meeting continued the series of preceding workshops held in 2002 in Napa, California and in 2003 in Montreux, Switzerland. The aim of the workshop was to bring together the existing ultrafast laser community and the emerging ultrafast X-ray community in order lo discuss recent scientific highlights from both fields and to outline new directions for the application of ultrafast X-rays. In turn, it was hoped that this would help define the source characteristics of future ultrafast X-ray sources such as X-ray Free Electron Lasers.

A correction to the article "Nearest-neighbor oxygen distances in liquid water and ice observed x-ray Raman based extended x-ray absorption fine structure," by Uwe Bergmann and colleagues, is presented.

A novel approach for monochromatizing and focussing the Vacuum-Ultraviolet and soft x-ray radiation from high-order harmonic generation of a femtosecond optical laser with only one optical element is presented. We demonstrate that off-axis reflection zone plates applied as focussing monochromators allow for efficiently optimizing the trade-off between energy resolution and temporal dispersion of the femtosecond pulses. In the current experimental realization, we show how the temporal dispersion can be varied between 2 fs and 16 fs with a correlating variation of the energy resolution EΔE between 20 and 90 for an off-axis reflection zone plate optimized for harmonic 13 at 20.41 eV. We also show how the focal spot size varies correspondingly between 80 × 90 μm2 and 290 × 140 μm2 as determined with a computational fitting approach based on a 3D Gaussian model. The diffraction efficiency for the tested zone plates amounts to up to 10%. We furthermore evaluate the influence of pointing stability on the performance of the zone plates. Based on our results we propose an optimized realization of a dedicated beam line for femtosecond pulses from high-order harmonic generation with an off-axis reflection zone plate. [ABSTRACT FROM AUTHOR]