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In this combined theoretical and experimental study we report on an analysis of the resonant inelastic X-ray scattering (RIXS) spectra of gas phase water via the lowest dissociative core-excited state |1s−1O4a11〉. We focus on the spectral feature near the dissociation limit of the electronic ground state. We show that the narrow atomic-like peak consists of the overlapping contribution from the RIXS channels back to the ground state and to the first valence excited state |1b−114a11〉 of the molecule. The spectral feature has signatures of ultrafast dissociation (UFD) in the core-excited state, as we show by means of ab initio calculations and time-dependent nuclear wave packet simulations. We show that the electronically elastic RIXS channel gives substantial contribution to the atomic-like resonance due to the strong bond length dependence of the magnitude and orientation of the transition dipole moment. By studying the RIXS for an excitation energy scan over the core-excited state resonance, we can understand and single out the molecular and atomic-like contributions in the decay to the lowest valence-excited state. Our study is complemented by a theoretical discussion of RIXS in the case of isotopically substituted water (HDO and D2O) where the nuclear dynamics is significantly affected by the heavier fragments' mass.
Understanding and controlling properties of transition metal complexes is a crucial step towards tailoring materials for sustainable energy applications. In a systematic approach, we use resonant inelastic X-ray scattering to study the influence of ligand substitution on the valence electronic structure around an aqueous iron(II) center. Exchanging cyanide with 2-2′-bipyridine ligands reshapes frontier orbitals in a way that reduces metal 3d charge delocalization onto the ligands. This net decrease of metal–ligand covalency results in lower metal-centered excited state energies in agreement with previously reported excited state dynamics. Furthermore, traces of solvent-effects were found indicating a varying interaction strength of the solvent with ligands of different character. Our results demonstrate how ligand exchange can be exploited to shape frontier orbitals of transition metal complexes in solution-phase chemistry; insights upon which future efforts can built when tailoring the functionality of photoactive systems for light-harvesting applications.
Local probes of the electronic ground state are essential for understanding hydrogen bonding in aqueous environments. When tuned to the dissociative core-excited state at the O1s pre-edge of water, resonant inelastic X-ray scattering back to the electronic ground state exhibits a long vibrational progression due to ultrafast nuclear dynamics. We show how the coherent evolution of the OH bonds around the core-excited oxygen provides access to high vibrational levels in liquid water. The OH bonds stretch into the long-range part of the potential energy curve, which makes the X-ray probe more sensitive than infra-red spectroscopy to the local environment. We exploit this property to effectively probe hydrogen bond strength via the distribution of intramolecular OH potentials derived from measurements. In contrast, the dynamical splitting in the spectral feature of the lowest valence-excited state arises from the short-range part of the OH potential curve and is rather insensitive to hydrogen bonding.
The phase diagram of water harbors controversial views on underlying structural properties of its constituting molecular moieties, its fluctuating hydrogen-bonding network, as well as pair-correlation functions. In this work, long energy-range detection of the X-ray absorption allows us to unambiguously calibrate the spectra for water gas, liquid, and ice by the experimental atomic ionization cross-section. In liquid water, we extract the mean value of 1.74 +/- 2.1% donated and accepted hydrogen bonds per molecule, pointing to a continuous-distribution model. In addition, resonant inelastic X-ray scattering with unprecedented energy resolution also supports continuous distribution of molecular neighborhoods within liquid water, as do X-ray emission spectra once the femtosecond scattering duration and proton dynamics in resonant X-ray-matter interaction are taken into account. Thus, X-ray spectra of liquid water in ambient conditions can be understood without a two-structure model, whereas the occurrence of nanoscale-length correlations within the continuous distribution remains open.
The dynamics of fragmentation and vibration of molecular systems with a large number of coupled degrees of freedom are key aspects for understanding chemical reactivity and properties. Here we present a resonant inelastic X-ray scattering (RIXS) study to show how it is possible to break down such a complex multidimensional problem into elementary components. Local multimode nuclear wave packets created by X-ray excitation to different core-excited potential energy surfaces (PESs) will act as spatial gates to selectively probe the particular ground-state vibrational modes and, hence, the PES along these modes. We demonstrate this principle by combining ultra-high resolution RIXS measurements for gas-phase water with state-of-the-art simulations.
Die Femtosekundendynamik nach resonanten Photoanregungen mit optischen und Röntgenpulsen ermöglicht eine selektive Verformung von chemischen N‐H‐ und N‐C‐Bindungen in 2‐Thiopyridon in wässriger Lösung. Die Untersuchung der orbitalspezifischen elektronischen Struktur und ihrer Dynamik auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung an der N1s‐Resonanz am Synchrotron und dem Freie‐Elektronen‐Laser LCLS in Kombination mit quantenchemischen Multikonfigurationsberechnungen erbringen den direkten Nachweis dieser kontrollierten photoinduzierten Molekülverformungen und ihrer ultrakurzen Zeitskala.
Die Femtosekundendynamik nach resonanten Photoanregungen mit optischen und Röntgenpulsen ermöglicht eine selektive Verformung von chemischen N‐H‐ und N‐C‐Bindungen in 2‐Thiopyridon in wässriger Lösung. Die Untersuchung der orbitalspezifischen elektronischen Struktur und ihrer Dynamik auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung an der N1s‐Resonanz am Synchrotron und dem Freie‐Elektronen‐Laser LCLS in Kombination mit quantenchemischen Multikonfigurationsberechnungen erbringen den direkten Nachweis dieser kontrollierten photoinduzierten Molekülverformungen und ihrer ultrakurzen Zeitskala.
The femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort time-scale.
We report on a combined theoretical and experimental study of core-excitation spectra of gas and liquid phase methanol as obtained with the use of X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). The electronic transitions are studied with computational methods that include strict and extended second-order algebraic diagrammatic construction [ADC(2) and ADC(2)-x], restricted active space second-order perturbation theory, and time-dependent density functional theory-providing a complete assignment of the near oxygen K-edge XAS. We show that multimode nuclear dynamics is of crucial importance for explaining the available experimental XAS and RIXS spectra. The multimode nuclear motion was considered in a recently developed "mixed representation" where dissociative states and highly excited vibrational modes are accurately treated with a time-dependent wave packet technique, while the remaining active vibrational modes are described using Franck-Condon amplitudes. Particular attention is paid to the polarization dependence of RIXS and the effects of the isotopic substitution on the RIXS profile in the case of dissociative core-excited states. Our approach predicts the splitting of the 2a RIXS peak to be due to an interplay between molecular and pseudo-atomic features arising in the course of transitions between dissociative core- and valence-excited states. The dynamical nature of the splitting of the 2a peak in RIXS of liquid methanol near pre-edge core excitation is shown. The theoretical results are in good agreement with our liquid phase measurements and gas phase experimental data available from the literature. (C) 2019 Author(s).
While extensive work has been dedicated to the measurement of the demagnetization time following an ultra-short laser pulse, experimental studies of its underlying microscopic mechanisms are still scarce. In transition metal ferromagnets, one of the main mechanism is the spin-flip of conduction electrons driven by electron-phonon scattering. Here, we present an original experimental method to monitor the electron-phonon mediated spin-flip scattering rate in nickel through the stringent atomic symmetry selection rules of x-ray emission spectroscopy. Increasing the phonon population leads to a waning of the 3d -> 2p(3/2) decay peak intensity, which reflects an increase of the angular momentum transfer scattering rate attributed to spin-flip. We find a spin relaxation time scale in the order of 50 fs in the 3d-band of nickel at room temperature, while consistantly, no such peak evolution is observed for the diamagnetic counterexample copper, using the same method.
The speciation of 2-Mercaptopyridine in aqueous solution has been investigated with nitrogen 1s Near Edge X-ray Absorption Fine Structure spectroscopy and time dependent Density Functional Theory. The prevalence of distinct species as a function of the solvent basicity is established. No indications of dimerization towards high concentrations are found. The determination of different molecular structures of 2-Mercaptopyridine in aqueous solution is put into the context of proton-transfer in keto-enol and thione-thiol tautomerisms. (C) 2016 The Authors. Published by Elsevier B.V.
The femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort time-scale.
In this combined theoretical and experimental study we report a full analysis of the resonant inelastic X-ray scattering (RIXS) spectra of H2O, D2O and HDO. We demonstrate that electronically-elastic RIXS has an inherent capability to map the potential energy surface and to perform vibrational analysis of the electronic ground state in multimode systems. We show that the control and selection of vibrational excitation can be performed by tuning the X-ray frequency across core-excited molecular bands and that this is clearly reflected in the RIXS spectra. Using high level ab initio electronic structure and quantum nuclear wave packet calculations together with high resolution RIXS measurements, we discuss in detail the mode coupling, mode localization and anharmonicity in the studied systems.
Hydration shells around ions are crucial for many fundamental biological and chemical processes. Their local physicochemical properties are quite different from those of bulk water and hard to probe experimentally. We address this problem by combining soft X-ray spectroscopy using a liquid jet and molecular dynamics (MD) simulations together with ab initio electronic structure calculations to elucidate the water ion interaction in a MgCl2 solution at the molecular level. Our results reveal that salt ions mainly affect the electronic properties of water molecules in close vicinity and that the oxygen K-edge X-ray emission spectrum of water molecules in the first solvation shell differs significantly from that of bulk water. Ion-specific effects are identified by fingerprint features in the water X-ray emission spectra. While Mg2+ ions cause a bathochromic shift of the water lone pair orbital, the 3p orbital of the Cl- ions causes an additional peak in the water emission spectrum at around 528 eV.
Thermally driven chemistry as well as materials’ functionality are determined by the potential energy surface of a systems electronic ground state. This makes the potential energy surface a central and powerful concept in physics, chemistry and materials science. However, direct experimental access to the potential energy surface locally around atomic centers and to its long-range structure are lacking. Here we demonstrate how sub-natural linewidth resonant inelastic soft x-ray scattering at vibrational resolution is utilized to determine ground state potential energy surfaces locally and detect long-range changes of the potentials that are driven by local modifications. We show how the general concept is applicable not only to small isolated molecules such as O2 but also to strongly interacting systems such as the hydrogen bond network in liquid water. The weak perturbation to the potential energy surface through hydrogen bonding is observed as a trend towards softening of the ground state potential around the coordinating atom. The instrumental developments in high resolution resonant inelastic soft x-ray scattering are currently accelerating and will enable broad application of the presented approach. With this multidimensional potential energy surfaces that characterize collective phenomena such as (bio)molecular function or high-temperature superconductivity will become accessible in near future.
The speciation of 2-Mercaptopyridine in aqueous solution has been investigated with nitrogen 1s Near Edge X-ray Absorption Fine Structure spectroscopy and time dependent Density Functional Theory. The prevalence of distinct species as a function of the solvent basicity is established. No indications of dimerization towards high concentrations are found. The determination of different molecular structures of 2-Mercaptopyridine in aqueous solution is put into the context of proton-transfer in keto-enol and thione-thiol tautomerisms. (C) 2016 The Authors. Published by Elsevier B.V.
In this combined theoretical and experimental study we report a full analysis of the resonant inelastic X-ray scattering (RIXS) spectra of H2O, D2O and HDO. We demonstrate that electronically-elastic RIXS has an inherent capability to map the potential energy surface and to perform vibrational analysis of the electronic ground state in multimode systems. We show that the control and selection of vibrational excitation can be performed by tuning the X-ray frequency across core-excited molecular bands and that this is clearly reflected in the RIXS spectra. Using high level ab initio electronic structure and quantum nuclear wave packet calculations together with high resolution RIXS measurements, we discuss in detail the mode coupling, mode localization and anharmonicity in the studied systems.
In this paper we report an experimental and computational study of liquid acetonitrile (H3C–C[triple bond, length as m-dash]N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the H2C–C[double bond, length as m-dash]NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS.
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.
The discovery of ultrafast X-ray induced optical reflectivity changes enabled the development of X-ray/optical cross correlation techniques at X-ray free electron lasers worldwide. We have now linked through experiment and theory the fundamental excitation and relaxation steps with the transient optical properties in finite solid samples. Therefore, we gain a thorough interpretation and an optimized detection scheme of X-ray induced changes to the refractive index and the X-ray/optical cross correlation response. (C) 2015 AIP Publishing LLC.
Liquid water molecules interact strongly with each other, forming a fluctuating hydrogen bond network and thereby giving rise to the anomalous phase diagram of liquid water. Consequently, symmetric and asymmetric water molecules have been found in the picosecond time average with IR and optical Raman spectroscopy. With subnatural linewidth resonant inelastic x-ray scattering (RIXS) at vibrational resolution, we take sub-femtosecond snapshots of the electronic and structural properties of water molecules in the hydrogen bond network. We derive a strong dominance of nonsymmetric molecules in liquid water in contrast to the gas phase on the sub-femtosecond timescale of RIXS and determine the fraction of highly asymmetrically distorted molecules.
Rydberg-Resolved Resonant Inelastic Soft X-Ray Scattering: Dynamics at Core Ionization Thresholds
(2015)
Resonant inelastic x-ray scattering spectra excited in the immediate vicinity of the core-level ionization thresholds of N-2 have been recorded. Final states of well-resolved symmetry-selected Rydberg series converging to valence-level ionization thresholds with vibrational excitations are observed. The results are well described by a quasi-two-step model which assumes that the excited electron is unaffected by the radiative decay. This threshold dynamics simplifies the interpretation of resonant inelastic x-ray scattering spectra considerably and facilitates characterization of low-energy excited final states in molecular systems.
In the current work, X-ray emission spectra of aqueous solutions of different inorganic salts within the Hofmeister series are presented. The results reflect the direct interaction of the ions with the water molecules and therefore, reveal general properties of the salt-water interactions. Within the experimental precision a significant effect of the ions on the water structure has been observed but no ordering according to the structure maker/structure breaker concept could be mirrored in the results indicating that the Hofmeister effect if existent may be caused by more complex interactions.
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.
Resonant inelastic soft x-ray scattering (RIXS) spectra excited at the 1 sigma(g) -> 3 sigma(u) resonance in gas-phase O-2 show excitations due to the nuclear degrees of freedom with up to 35 well-resolved discrete vibronic states and a continuum due to the kinetic energy distribution of the separated atoms. The RIXS profile demonstrates spatial quantum beats caused by two interfering wave packets with different momenta as the atoms separate. Thomson scattering strongly affects both the spectral profile and the scattering anisotropy.
Amorphous materials represent a large and important emerging area of material's science. Amorphous oxides are key technological oxides in applications such as a gate dielectric in Complementary metal-oxide semiconductor devices and in Silicon-Oxide-Nitride-Oxide-Silicon and TANOS (TaN-Al2O3-Si3N4-SiO2-Silicon) flash memories. These technologies are required for the high packing density of today's integrated circuits. Therefore the investigation of defect states in these structures is crucial. In this work we present X-ray synchrotron measurements, with an energy resolution which is about 5-10 times higher than is attainable with standard spectrometers, of amorphous alumina. We demonstrate that our experimental results are in agreement with calculated spectra of amorphous alumina which we have generated by stochastic quenching. This first principles method, which we have recently developed, is found to be superior to molecular dynamics in simulating the rapid gas to solid transition that takes place as this material is deposited for thin film applications. We detect and analyze in detail states in the band gap that originate from oxygen pairs. Similar states were previously found in amorphous alumina by other spectroscopic methods and were assigned to oxygen vacancies claimed to act mutually as electron and hole traps. The oxygen pairs which we probe in this work act as hole traps only and will influence the information retention in electronic devices. In amorphous silica oxygen pairs have already been found, thus they may be a feature which is characteristic also of other amorphous metal oxides.
Resonant inelastic soft x-ray scattering spectra excited at the dissociative 1 sigma(g) -> 3 sigma(u) resonance in gas-phase O(2) are presented and discussed in terms of state-of-the-art molecular theory. A new selection rule due to internal spin coupling is established, facilitating a deep analysis of the valence excited final states. Furthermore, it is found that a commonly accepted symmetry selection rule due to orbital parity breaks down, as the core hole and excited electron swap parity, thereby opening the symmetry forbidden 3 sigma(g) decay channel.
Resonant inelastic x-ray scattering spectra excited at the O1s(-1)pi* resonance of liquid acetone are presented. Scattering to the electronic ground state shows a resolved vibrational progression where the dominant contribution is due to the C-O stretching mode, thus demonstrating a unique sensitivity of the method to the local potential energy surface in complex molecular systems. For scattering to electronically excited states, soft vibrational modes and, to a smaller extent, intermolecular interactions give a broadening, which blurs the vibrational fine structure. It is predicted that environmental broadening is dominant in aqueous acetone.
A detailed study of inelastic x-ray scattering from the ground state to the (3)Sigma(g)(3 sigma(-1)(g)3s(g)(1)) state of the O-2 molecule is presented. The observed angular anisotropy shows that the vibrational excitations within this final state are strongly dependent on the polarization of the incident radiation. The analysis demonstrates that this is a manifestation of interference between resonant and direct nonresonant inelastic x-ray scattering. This interference provides a new tool to monitor nuclear dynamics by relative rotation of the polarization vectors of the incident and scattered photons.
Inelastic x-ray scattering spectra excited at the 1s(-1) pi* resonance of gas phase O-2 have been recorded with an overall energy resolution that allows for well-resolved vibrational progressions. The nuclear wave packet dynamics in the intermediate state is reflected in vibrational excitations of the electronic ground state, and by fine-tuning the excitation energy the dissociation dynamics in the predissociative B' (3) Pi(g) final state is controlled.