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Symmetry and its breaking crucially define the chemical properties of molecules and their functionality. Resonant inelastic X-ray scattering is a local electronic structure probe reporting on molecular symmetry and its dynamical breaking within the femtosecond scattering duration. Here, we study pyrimidine, a system from the C-2v point group, in an aqueous solution environment, using scattering though its 2a(2) resonance. Despite the absence of clean parity selection rules for decay transitions from in-plane orbitals, scattering channels including decay from the 7b(2) and 11a(1) orbitals with nitrogen lone pair character are a direct probe for molecular symmetry. Computed spectra of explicitly solvated molecules sampled from a molecular dynamics simulation are combined with the results of a quantum dynamical description of the X-ray scattering process. We observe dominant signatures of core-excited Jahn-Teller induced symmetry breaking for resonant excitation. Solvent contributions are separable by shortening of the effective scattering duration through excitation energy detuning.
The simultaneous detection of energy, momentum and temporal information in electron spectroscopy is the key aspect to enhance the detection efficiency in order to broaden the range of scientific applications. Employing a novel 60 degrees wide angle acceptance lens system, based on an additional accelerating electron optical element, leads to a significant enhancement in transmission over the previously employed 30 degrees electron lenses. Due to the performance gain, optimized capabilities for time resolved electron spectroscopy and other high transmission applications with pulsed ionizing radiation have been obtained. The energy resolution and transmission have been determined experimentally utilizing BESSY II as a photon source. Four different and complementary lens modes have been characterized. (C) 2017 The Authors. Published by Elsevier B.V.
The simultaneous detection of energy, momentum and temporal information in electron spectroscopy is the key aspect to enhance the detection efficiency in order to broaden the range of scientific applications. Employing a novel 60 degrees wide angle acceptance lens system, based on an additional accelerating electron optical element, leads to a significant enhancement in transmission over the previously employed 30 degrees electron lenses. Due to the performance gain, optimized capabilities for time resolved electron spectroscopy and other high transmission applications with pulsed ionizing radiation have been obtained. The energy resolution and transmission have been determined experimentally utilizing BESSY II as a photon source. Four different and complementary lens modes have been characterized. (C) 2017 The Authors. Published by Elsevier B.V.
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.
The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free electron laser to directly observe the decreased bonding antibonding splitting following bond-activation using an ultrashort optical laser pulse.
We prove the hitherto hypothesized sequential dissociation of Fe(CO)(5) in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)(4) within the temporal resolution of the experiment and further to Fe(CO)(3) within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3) showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)(5) complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transition metals in photochemical reactions of coordination complexes. Published by AIP Publishing.
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.
Charge-density rearrangements after metal-to-ligand charge-transfer excitation in an iron photosensitizer are investigated by R. M Jay, A. Fohlisch et al. in their Communication (DOI: 10.1002/anie.201904761). By using time-resolved X-ray absorption spectroscopy, surprising covalency-effects are revealed that inhibit charge-separation at the intra-molecular level. Furthermore, the underlying mechanism is proposed to be generally in effect for all commonly used photosensitizers in light-harvesting applications, which challenges the common perception of electronic charge-transfer.
The fluctuating hydrogen bridge bonded network of liquid water at ambient conditions entails a varied ensemble of the underlying constituting H2O molecular moieties. This is mirrored in a manifold of the H2O molecular potentials. Subnatural line width resonant inelastic X-ray scattering allowed us to quantify the manifold of molecular potential energy surfaces along the H2O symmetric normal mode and the local asymmetric O-H bond coordinate up to 1 and 1.5 angstrom, respectively. The comparison of the single H2O molecular potentials and spectroscopic signatures with the ambient conditions liquid phase H2O molecular potentials is done on various levels. In the gas phase, first principles, Morse potentials, and stepwise harmonic potential reconstruction have been employed and benchmarked. In the liquid phase the determination of the potential energy manifold along the local asymmetric O-H bond coordinate from resonant inelastic X-ray scattering via the bound state oxygen ls to 4a(1) resonance is treated within these frameworks. The potential energy surface manifold along the symmetric stretch from resonant inelastic X-ray scattering via the oxygen 1 s to 2b(2) resonance is based on stepwise harmonic reconstruction. We find in liquid water at ambient conditions H2O molecular potentials ranging from the weak interaction limit to strongly distorted potentials which are put into perspective to established parameters, i.e., intermolecular O-H, H-H, and O-O correlation lengths from neutron scattering.
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.
The layered dichalcogenide MoS2 is relevant for electrochemical Li adsorption/intercalation, in the course of which the material undergoes a concomitant structural phase transition from semiconducting 2H-MoS2 to metallic 1T-LixMoS2. With the core hole clock approach at the S L1 X-ray absorption edge we quantify the ultrafast directional charge transfer of excited S3p electrons in-plane () and out-of-plane (perpendicular to) for 2H-MoS2 as tau 2H,=0.38 +/- 0.08 fs and tau 2H,perpendicular to =0.33 +/- 0.06 fs and for 1T-LixMoS2 as tau 1T,=0.32 +/- 0.12 fs and tau 1T,perpendicular to =0.09 +/- 0.07 fs. The isotropic charge delocalization of S3p electrons in the semiconducting 2H phase within the S-Mo-S sheets is assigned to the specific symmetry of the Mo-S bonding arrangement. Formation of 1T-LixMoS2 by lithiation accelerates the in-plane charge transfer by a factor of similar to 1.2 due to electron injection to the Mo-S covalent bonds and concomitant structural repositioning of S atoms within the S-Mo-S sheets. For excitation into out-of-plane orbitals, an accelerated charge transfer by a factor of similar to 3.7 upon lithiation occurs due to S-Li coupling.
For the layered transition metal dichalcogenide 1T-TaS2, we establish through a unique experimental approach and density functional theory, how ultrafast charge transfer in 1T-TaS2 takes on isotropic three-dimensional character or anisotropic two-dimensional character, depending on the commensurability of the charge density wave phases of 1T-TaS2. The X-ray spectroscopic core-hole-clock method prepares selectively in-and out-of-plane polarized sulfur 3p orbital occupation with respect to the 1T-TaS2 planes and monitors sub-femtosecond wave packet delocalization. Despite being a prototypical two-dimensional material, isotropic three-dimensional charge transfer is found in the commensurate charge density wave phase (CCDW), indicating strong coupling between layers. In contrast, anisotropic two-dimensional charge transfer occurs for the nearly commensurate phase (NCDW). In direct comparison, theory shows that interlayer interaction in the CCDW phase - not layer stacking variations - causes isotropic three-dimensional charge transfer. This is presumably a general mechanism for phase transitions and tailored properties of dichalcogenides with charge density waves.
Core-level spectra of liquids can be difficult to interpret due to the presence of a range of local environments. We present computational methods for investigating core-level spectra based on the idea that both local structural parameters and the x-ray spectra behave as functions of the local atomic configuration around the absorbing site. We identify correlations between structural parameters and spectral intensities in defined regions of interest, using the oxygen K-edge excitation spectrum of liquid water as a test case. Our results show that this kind of analysis can find the main structure-spectral relationships of ice, liquid water, and supercritical water.
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.
Determining covalent and charge-transfer contributions to bonding in solution has remained an experimental challenge. Here, the quenching of fluorescence decay channels as expressed in dips in the L-edge X-ray spectra of solvated 3d transition-metal ions and complexes was reported as a probe. With a full set of experimental and theoretical ab initio L-edge X-ray spectra of aqueous Cr3+, including resonant inelastic X-ray scattering, we address covalency and charge transfer for this prototypical transition-metal ion in solution. We dissect local atomic effects from intermolecular interactions and quantify X-ray optical effects. We find no evidence for the asserted ultrafast charge transfer to the solvent and show that the dips are readily explained by X-ray optical effects and local atomic state dependence of the fluorescence yield. Instead, we find, besides ionic interactions, a covalent contribution to the bonding in the aqueous complex of ligand-to-metal charge-transfer character.
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 electronic and magnetic excitations of bulk NiO have been determined using the 3A2g to 3T2g crystal-field transition at the Ni M2,3 edges with resonant inelastic x-ray scattering at 66.3- and 67.9-eV photon energies and 33-meV spectral resolution. Unambiguous assignment of the high-energy side of this state to a spin-flip satellite is achieved. We extract an effective exchange field of 89±4 meV in the 3T2g excited final state from empirical two-peak spin-flip model. The experimental data is found consistent with crystal-field model calculations using exchange fields of 60–100 meV. Full agreement with crystal-field multiplet calculations is achieved for the incident photon energy dependence of line shapes. The lower exchange parameter in the excited state as compared to the ground-state value of 120 meV is discussed in terms of the modification of the orbital occupancy (electronic effects) and of the structural dynamics: (A) With pure electronic effects, the lower exchange energy is attributed to the reduction in effective hopping integral. (B) With no electronic effects, we use the S = 1 Heisenberg model of antiferromagnetism to derive a second-nearest-neighbor exchange constant J2 = 14.8±0.6 meV. Based on the linear correlation between J2 and the lattice parameter from pressure-dependent experiments, an upper limit of 2% local Ni-O bond elongation during the femtosecond scattering duration is derived.
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.