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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. (C) 2017 Author(s).
Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal-ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. pi-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences sigma-donation. Our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.
X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. However, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. Here we compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based on self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. We show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements. (C) 2016 Optical Society of America
Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes Mn-II(acac)(2) and Mn-III(acac)(3) as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of Mn-III in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways.
X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn similar to 6-15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions. (C) 2017 Author(s).
Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics
(2016)
Ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbital and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)(5) in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given-which will be covered experimentally by upcoming transform-limited x-ray sources.
Bonding of the Ni2+(aq) complex is investigated with an unprecedented combination of resonant inelastic X-ray scattering (RIXS) measurements and ab initio calculations at the Ni L absorption edge. The spectra directly reflect the relative energies of the ligand-field and charge-transfer valence-excited states. They give element-specific access with atomic resolution to the ground-state electronic structure of the complex and allow quantification of ligand-field strength and 3d-3d electron correlation interactions in the Ni2+(aq) complex. The experimentally determined ligand-field strength is 10Dq = 1.1 eV. This and the Racah parameters characterizing 3d-3d Coulomb interactions B = 0.13 eV and C = 0.42 eV as readily derived from the measured energies match very well with the results from UV-vis spectroscopy. Our results demonstrate how L-edge RIXS can be used to complement existing spectroscopic tools for the investigation of bonding in 3d transition-metal coordination compounds in solution. The ab initio RASPT2 calculation is successfully used to simulate the L-edge RIXS spectra.
A setup for resonant inelastic soft x-ray scattering on liquids at free electron laser light sources
(2012)
We present a flexible and compact experimental setup that combines an in vacuum liquid jet with an x-ray emission spectrometer to enable static and femtosecond time-resolved resonant inelastic soft x-ray scattering (RIXS) measurements from liquids at free electron laser (FEL) light sources. We demonstrate the feasibility of this type of experiments with the measurements performed at the Linac Coherent Light Source FEL facility. At the FEL we observed changes in the RIXS spectra at high peak fluences which currently sets a limit to maximum attainable count rate at FELs. The setup presented here opens up new possibilities to study the structure and dynamics in liquids.
The valence-excited states of ferric and ferrous hexacyanide ions in aqueous solution were mapped by resonant inelastic X-ray scattering (RIXS) at the Fe L-2,L-3 and N K edges. Probing of both the central Fe and the ligand N atoms enabled identification of the metal-and ligand-centered excited states, as well as ligand-to-metal and metal-to-ligand charge-transfer excited states. Ab initio calculations utilizing the RASPT2 method were used to simulate the Fe L-2,L-3-edge RIXS spectra and enabled quantification of the covalencies of both occupied and empty orbitals of pi and sigma symmetry. We found that pi back-donation in the ferric complex is smaller than that in the ferrous complex. This is evidenced by the relative amounts of Fe 3d character in the nominally 2 pi CN- molecular orbital of 7% and 9% in ferric and ferrous hexacyanide, respectively. Utilizing the direct sensitivity of Fe L-3-edge RIXS to the Fe 3d character in the occupied molecular orbitals, we also found that the donation interactions are dominated by sigma bonding. The latter was found to be stronger in the ferric complex, with an Fe 3d contribution to the nominally 5 sigma CN- molecular orbitals of 29% compared to 20% in the ferrous complex. These results are consistent with the notion that a higher charge at the central metal atom increases donation and decreases back-donation.
The prototypical photoinduced dissociation of Fe(CO)(5) in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO)(5) successively dissociates to Fe(CO)(4) and Fe(CO)(3) along a pathway where both fragments retain the singlet multiplicity of Fe(CO)(5). The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO)(4) and Fe(CO)(3) with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valenceorbital interactions upon Fe-CO dissociation, thereby validating fundamental theoretical concepts in Fe-CO bonding. Chemical shifts of CO 3 sigma inner-valence and Fe 3 sigma core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent charge localization and core-hole screening based on calculated changes in electron densities upon core-hole creation in the final ionic states. This extends the established capabilities of steady-state electron spectroscopy for chemical analysis to time-resolved investigations. It could also serve as a benchmark for howcharge and spin density changes in molecular dissociation and excited-state dynamics are expressed in valence and core-level photoelectron spectroscopy. Published by AIP Publishing.
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 degrees C and +50 degrees C. The setup enables to record soft x-ray absorption spectra of liquids in transmission mode with a temperature resolution of 0.5K 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. (C) 2014 AIP Publishing LLC.
Total and partial fluorescence yield (PFY) L-edge x-ray absorption spectra differ from the transmission x-ray absorption spectra (XAS) through state-dependent fluorescence yield across the XAS. For 3d(1) to 3d(9) in octahedral symmetry we apply simulations of PFY and XAS and show how the atomic 2p3d Coulomb exchange parameter G(pd) governs the differences in the L-3/(L-2 + L-3) branching ratio between PFY and XAS. G(pd) orders the XAS final states following Hund's rules creating a strong state-dependent fluorescence decay strength variation across the XAS leading to the differences between PFY and XAS.
L-edge spectroscopy of 3d transition metals provides important electronic structure information and has been used in many fields. However, the use of this method for studying dilute aqueous systems, such as metalloenzymes, has not been prevalent because of severe radiation damage and the lack of suitable detection systems. Here we present spectra from a dilute Mn aqueous solution using a high-transmission zone-plate spectrometer at the Linac Coherent Light Source (LCLS). The spectrometer has been optimized for discriminating the Mn L-edge signal from the overwhelming 0 K-edge background that arises from water and protein itself, and the ultrashort LCLS X-ray pulses can outrun X-ray induced damage. We show that the deviations of the partial-fluorescence yield-detected spectra from the true absorption can be well modeled using the state-dependence of the fluorescence yield, and discuss implications for the application of our concept to biological samples.
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.
While ubiquitous, the making and breaking of hydrogen bonds in solution is notoriously difficult to study due to the associated complex changes of nuclear and electronic structures. With the aim to reduce the according uncertainty in correlating experimental observables and hydrogen-bond configurations, we combine the information from proximate methods to study the N-H center dot center dot center dot O hydrogen bond in solution. We investigate hydrogen-bonding of the N-H group of N-methylaniline with oxygen from liquid DMSO and acetone with infrared spectra in the N-H stretching region and X-ray absorption spectra at the N K-edge. We experimentally observe blue shifts of the infrared stretching band and an X-ray absorption pre-edge peak when going from DMSO to acetone. With ab initio molecular dynamics simulations and calculated spectra, we qualitatively reproduce the experimental observables but we do not reach quantitative agreement with experiment. The infrared spectra support the notion of weakening the N-H center dot center dot center dot O hydrogen bond from DMSO to acetone. However, we fail to theoretically reproduce the measured shift of the X-ray absorption pre-edge peak. We discuss possible shortcomings of the simulation models and spectrum calculations. Common features and distinct differences with the O-H center dot center dot center dot O hydrogen bond are highlighted, and the implications for monitoring hydrogen-bond breaking in solution are discussed.
We report on oxygen K-edge soft x-ray emission spectroscopy from a liquid water jet at the Linac Coherent Light Source. We observe significant changes in the spectral content when tuning over a wide range of incident x-ray fluences. In addition the total emission yield decreases at high fluences. These modifications result from reabsorption of x-ray emission by valence-excited molecules generated by the Auger cascade. Our observations have major implications for future x-ray emission studies at intense x-ray sources. We highlight the importance of the x-ray pulse length with respect to the core-hole lifetime.
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 tau(dyn) = 1.2 +/- 0.8 fs. By detuning the excitation energy below the absorption resonance we reduce the effective scattering time below sdyn, 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. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.
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. Published by AIP Publishing.
The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (T-H) of similar to 232 K [J. A. Sellberg et al., Nature 510, 381-384 (2014)]. Here, we utilize a similar approach to study the structure of bulk liquid water below T-H using oxygen K-edge x-ray emission spectroscopy (XES). Based on previous XES experiments [T. Tokushima et al., Chem. Phys. Lett. 460, 387-400 (2008)] at higher temperatures, we expected the ratio of the 1b(1)' and 1b(1)" peaks associated with the lone-pair orbital in water to change strongly upon deep supercooling as the coordination of the hydrogen (H-) bonds becomes tetrahedral. In contrast, we observed only minor changes in the lone-pair spectral region, challenging an interpretation in terms of two interconverting species. A number of alternative hypotheses to explain the results are put forward and discussed. Although the spectra can be explained by various contributions from these hypotheses, we here emphasize the interpretation that the line shape of each component changes dramatically when approaching lower temperatures, where, in particular, the peak assigned to the proposed disordered component would become more symmetrical as vibrational interference becomes more important. (C) 2015 AIP Publishing LLC.