Search

Quantifying charge delocalization associated with short-lived photoexcited states of molecular complexes in solution remains experimentally challenging, requiring local element specific femtosecond experimental probes of time-evolving electron transfer. In this study, we quantify the evolving valence hole charge distribution in the photoexcited charge transfer state of a prototypical mixed valence bimetallic iron-ruthenium complex, [(CN)5FeIICNRuIII(NH3)5]-, in water by combining femtosecond X-ray spectroscopy measurements with time-dependent density functional theory calculations of the excited-state dynamics. We estimate the valence hole charge that accumulated at the Fe atom to be 0.6 ± 0.2, resulting from excited-state metal-to-metal charge transfer, on an ∼60 fs time scale. Our combined experimental and computational approach provides a spectroscopic ruler for quantifying excited-state valency in solvated complexes.

The metal centres in metalloenzymes and molecular catalysts are responsible for the rearrangement of atoms and electrons during complex chemical reactions, and they enable selective pathways of charge and spin transfer, bond breaking/making and the formation of new molecules. Mapping the electronic structural changes at the metal sites during the reactions gives a unique mechanistic insight that has been difficult to obtain to date. The development of X-ray free-electron lasers (XFELs) enables powerful new probes of electronic structure dynamics to advance our understanding of metalloenzymes. The ultrashort, intense and tunable XFEL pulses enable X-ray spectroscopic studies of metalloenzymes, molecular catalysts and chemical reactions, under functional conditions and in real time. In this Technical Review, we describe the current state of the art of X-ray spectroscopy studies at XFELs and highlight some new techniques currently under development. With more XFEL facilities starting operation and more in the planning or construction phase, new capabilities are expected, including high repetition rate, better XFEL pulse control and advanced instrumentation. For the first time, it will be possible to make real-time molecular movies of metalloenzymes and catalysts in solution, while chemical reactions are taking place.

With flexibility in tuning their electric and magnetic properties, multiferroics can be used in information exchange and storage in ways that are very different from the present electronic materials. Here we use resonant soft X-ray scattering spectroscopy to study the F-type (0,τ,0) and C-type (0, 1–2τ, 0) diffraction peaks from sinusoidal antiferromagnetic spin order in multiferroic DyMnO3. By comparing the temperature dependence of ordering wave vectors τ, peak intensities I, and correlation lengths λ measured at Mn L2-, O K-, and Dy M5-edges, we show that the nearly perfect locking between the ordering wave vectors from Dy 4f states and Mn 3d orbitals manifesting the second harmonic diffraction peak implies the notable orbital involvement in the coupling between Mn and Dy spins. Our DFT calculations further suggest that the lattice response to different antiferromagnetic ground states (A-type versus E-type) is much weaker in TbMnO3, in agreement with previous claim that the symmetric exchange interaction can be an important factor for understanding the ferroelectricity in DyMnO3 than in TbMnO3.

We present a joint experimental and computational study of the hexacyanoferrate aqueous complexes at equilibrium in the 250 meV to 7.15 keV regime. The experiments and the computations include the vibrational spectroscopy of the cyanide ligands, the valence electronic absorption spectra, and Fe 1s core hole spectra using element-specific-resonant X-ray absorption and emission techniques. Density functional theory-based quantum mechanics/molecular mechanics molecular dynamics simulations are performed to generate explicit solute-solvent configurations, which serve as inputs for the spectroscopy calculations of the experiments spanning the IR to X-ray wavelengths. The spectroscopy simulations are performed at the same level of theory across this large energy window, which allows for a systematic comparison of the effects of explicit solute-solvent interactions in the vibrational, valence electronic, and core-level spectra of hexacyanoferrate complexes in water. Although the spectroscopy of hexacyanoferrate complexes in solution has been the subject of several studies, most of the previous works have focused on a narrow energy window and have not accounted for explicit solute-solvent interactions in their spectroscopy simulations. In this work, we focus our analysis on identifying how the local solvation environment around the hexacyanoferrate complexes influences the intensity and line shape of specific spectroscopic features in the UV/vis, X-ray absorption, and valence-to-core X-ray emission spectra. The identification of these features and their relationship to solute-solvent interactions is important because hexacyanoferrate complexes serve as model systems for understanding the photochemistry and photophysics of a large class of Fe(II) and Fe(III) complexes in solution.

Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (∼2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400 nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps) and decays within 6 ns. The second transient species forms on a timescale of ∼400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowest-lying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems.

We applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ∼70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemical reaction pathways and transient products of sulfur-containing molecules in solution.

Understanding interfacial charge-transfer processes on the atomic level is crucial to support the rational design of energy-challenge relevant systems such as solar cells, batteries, and photocatalysts. A femtosecond time-resolved core-level photoelectron spectroscopy study is performed that probes the electronic structure of the interface between ruthenium-based N3 dye molecules and ZnO nanocrystals within the first picosecond after photoexcitation and from the unique perspective of the Ru reporter atom at the center of the dye. A transient chemical shift of the Ru 3d inner-shell photolines by (2.3 ± 0.2) eV to higher binding energies is observed 500 fs after photoexcitation of the dye. The experimental results are interpreted with the aid of ab initio calculations using constrained density functional theory. Strong indications for the formation of an interfacial charge-transfer state are presented, providing direct insight into a transient electronic configuration that may limit the efficiency of photoinduced free charge-carrier generation.

Controlling a phase of matter by coherently manipulating specific vibrational modes has long been an attractive (yet elusive) goal for ultrafast science. Solids with strongly correlated electrons, in which even subtle crystallographic distortions can result in colossal changes of the electronic and magnetic properties, could be directed between competing phases by such selective vibrational excitation. In this way, the dynamics of the electronic ground state of the system become accessible, and new insight into the underlying physics might be gained. Here we report the ultrafast switching of the electronic phase of a magnetoresistive manganite via direct excitation of a phonon mode at 71 meV (17 THz). A prompt, five-order-of-magnitude drop in resistivity is observed, associated with a non-equilibrium transition from the stable insulating phase to a metastable metallic phase. In contrast with light-induced, and current-driven phase transitions, the vibrationally driven bandgap collapse observed here is not related to hot-carrier injection and is uniquely attributed to a large-amplitude Mn-O distortion. This corresponds to a perturbation of the perovskite-structure tolerance factor, which in turn controls the electronic bandwidth via inter-site orbital overlap. Phase control by coherent manipulation of selected metal--oxygen phonons should find extensive application in other complex solids--notably in copper oxide superconductors, in which the role of Cu-O vibrations on the electronic properties is currently controversial.

Interaction of an electron beam with a femtosecond laser pulseco-propagating through a wiggler modulates the electronenergies within a short slice of the electron bunch comparable with the duration of the laser pulse (Figure 1). Propagating around an electron storage ring, this bunch develops a longitudinal density perturbation due to the dispersion of electron trajectories. Figure 1 shows how this creates femtosecond electron bunch wings which are used for femtosecond x-ray light. In addition, this density perturbation emits temporally and spatially coherent tera-hertz pulses whichare inherently synchronized to the modulating laser. This gives us a new way to study coherent synchrotron radaition, and creates an opportunity for tuning the THz emmission specifically for the needs of a given experiment.

Most existing electron sources extract electrons from conductors. Since the actual temperature inside the conductor is much less than the Fermi temperature of the conduction electrons, the electron degeneracy (delta_f) is close to 1, the maximum allowed by the Pauli exclusion principle. However, during extraction several factors conspire together to reduce delta_f many orders of magnitude, limiting the achieved values to approx 10-5. A new concept is described for building a novel electron source designed to produce a pulsed beam with delta_f approx 2~;10-3 and longitudinal emittance four orders of magnitude smaller than currently achieved values. This high brightness, low longitudinal emittance regime enables a wide range of novel applications that utilize angstrom-scale spatial resolution and eV-scale energy resolution. The current state of a proof-of-principle experiment conducted at LBNL is also described.

At the Advanced Light Source (ALS), the 'femtoslicing' beamline is in operation since 1999 for the production of x-ray synchrotron radiation pulses with femtosecond duration. The mechanism used for generating the short x-ray pulses induces at the same time temporary structures in the electron bunch longitudinal distribution with very short characteristic length. Such structures emit intense coherent synchrotron radiation (CSR) in the terahertz frequency range. These CSR pulses were first observed at the ALS, and the measurement of their intensity is now routinely used as a diagnostics for the tune-up of the femtoslicing x-ray experiments. At the same time, these CSR pulses synchronous with the modulating laser, represent a potential source of terahertz radiation with very interesting features. Several measurements have been performed for their characterization and in this paper we present an updated description of the experimental results and of their interpretation. In particular, we include more data on the interesting interaction, previously observed at the ALS, between the slicing and the microbunching instability (MBI), where under particular circumstances, the slicing seems to trigger the onset of the instability.

We directly measure the photoinduced insulator-to-metal transition in VO2 using time-resolved near-edge x-ray absorption. Picosecond pulses of synchrotron radiation are used to detect the redshift in the vanadium L3edge at 516 eV, which is associated with the transient collapse of the low-temperature band gap. We identify a two-component temporal response, corresponding to an ultrafast transformation over a 50 nm surface layer, followed by 40 m/s thermal growth of the metallic phase into the bulk.

Femtosecond x-ray pump–x-ray probe experiments are currently possible at free electron lasers such as the linac coherent light source, which opens new opportunities for studying solvated transition metal complexes. In order to make the most effective use of these kinds of experiments, it is necessary to determine which chemical properties an x-ray probe pulse will measure. We have combined electron cascade calculations and excited-state time-dependent density functional theory calculations to predict the initial state prepared by an x-ray pump and the subsequent x-ray probe spectra at the Fe K-edge in the solvated model transition metal complex, K4FeII(CN)6. We find several key spectral features that report on the ligand-field splitting and the 3p and 3d electron interactions. We then show how these features could be measured in an experiment. [ABSTRACT FROM AUTHOR]

We report on the UV-induced photochemistry of the biologically relevant sulfur-containing thiol group and the disulfide bond in solution using picosecond X-ray absorption spectroscopy at the sulfur K-edge. This study provides element-specific insight into the 267-nm induced photo-chemistry of two model compounds, an aromatic thiol and an aliphatic disulfide. Our transient spectra point to two primary and several secondary photoproducts, and our analysis may aid in understanding UV damage in proteins.

We report the first time-resolved spectroscopy of aqueous solution in the Xray water window. Nitrogen K-edge spectra, combined with ab initio calculations, reveal distinct charge delocalization, shedding light on the origins of ultrafast spin crossover.

Aproposed method to enhance 13 femtosecond 625 nanometer wavelength pulses to twice these rates as well as produce 11 fs 312 nm ultraviolet pulses and factor ten picoJoules energies uses a 2.5 micrometer thin film. The thin medium is a nonlinear poled polymeric film with very small group velocity mismatch for enhancement purposes. Results support the use of poled polymer film for enhancement of pulse rates since this medium possess characteristics which make them suited for nonlinear optical applications.

We present the first femtosecond soft x-ray spectroscopy in liquids, enabling the observation of changes in hydrogen bond structures in water via core-hole excitation. The oxygen K-edge of vibrationally excited water is probed with femtosecond soft x-ray pulses, exploiting the relation between different water structures and distinct x-ray spectral features. After excitation of the intramolecular OH stretching vibration, characteristic x-ray absorption changes monitor the conversion of strongly hydrogen-bonded water structures to more disordered structures with weaker hydrogen-bonding described by a single subpicosecond time constant. The latter describes the thermalization time of vibrational excitations and defines the characteristic maximum rate with which nonequilibrium populations of more strongly hydrogen-bonded water structures convert to less-bonded ones. On short time scales, the relaxation of vibrational excitations leads to a transient high-pressure state and a transient absorption spectrum different from that of statically heated water. [ABSTRACT FROM AUTHOR]