Disentangling the evolution of electrons and holes in photoexcited ZnO nanoparticles.

The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy, and ab initio molecular dynamics (MD) simulations. The photoluminescence is excited at 4.66 eV, well above the band edge, and shows that electron cooling in the conduction band and exciton formation occur in <500 fs, in excellent agreement with theoretical predictions. The x-ray absorption measurements, obtained upon excitation close to the band edge at 3.49 eV, are sensitive to the migration and trapping of holes. They reveal that the 2 ps transient largely reproduces the previously reported transient obtained at 100 ps time delay in synchrotron studies. In addition, the x-ray absorption signal is found to rise in ∼1.4 ps, which we attribute to the diffusion of holes through the lattice prior to their trapping at singly charged oxygen vacancies. Indeed, the MD simulations show that impulsive trapping of holes induces an ultrafast expansion of the cage of Zn atoms in <200 fs, followed by an oscillatory response at a frequency of ∼100 cm-1, which corresponds to a phonon mode of the system involving the Zn sub-lattice.

Ten-Fold Solvent Kinetic Isotope Effect for the Nonradiative Relaxation of the Aqueous Ferrate(VI) Ion.

Hypervalent iron intermediates have been invoked in the catalytic cycles of many metalloproteins, and thus, it is crucial to understand how the coupling between such species and their environment can impact their chemical and physical properties in such contexts. In this work, we take advantage of the solvent kinetic isotope effect (SKIE) to gain insight into the nonradiative deactivation of electronic excited states of the aqueous ferrate(VI) ion. We observe an exceptionally large SKIE of 9.7 for the nanosecond-scale relaxation of the lowest energy triplet ligand field state to the ground state. Proton inventory studies demonstrate that a single solvent O-H bond is coupled to the ion during deactivation, likely due to the sparse vibrational structure of ferrate(VI). Such a mechanism is consistent with that reported for the deactivation of f-f excited states of aqueous trivalent lanthanides, which exhibit comparably large SKIE values. This phenomenon is ascribed entirely to dissipation of energy into a higher overtone of a solvent acceptor mode, as any impact on the apparent relaxation rate due to a change in solvent viscosity is negligible.

Asynchronous x-ray multiprobe data acquisition for x-ray transient absorption spectroscopy.

Laser pump X-ray Transient Absorption (XTA) spectroscopy offers unique insights into photochemical and photophysical phenomena. X-ray Multiprobe data acquisition (XMP DAQ) is a technique that acquires XTA spectra at thousands of pump-probe time delays in a single measurement, producing highly self-consistent XTA spectral dynamics. In this work, we report two new XTA data acquisition techniques that leverage the high performance of XMP DAQ in combination with High Repetition Rate (HRR) laser excitation: HRR-XMP and Asynchronous X-ray Multiprobe (AXMP). HRR-XMP uses a laser repetition rate up to 200 times higher than previous implementations of XMP DAQ and proportionally increases the data collection efficiency at each time delay. This allows HRR-XMP to acquire more high-quality XTA data in less time. AXMP uses a frequency mismatch between the laser and x-ray pulses to acquire XTA data at a flexibly defined set of pump-probe time delays with a spacing down to a few picoseconds. AXMP introduces a novel pump-probe synchronization concept that acquires data in clusters of time delays. The temporally inhomogeneous distribution of acquired data improves the attainable signal statistics at early times, making the AXMP synchronization concept useful for measuring sub-nanosecond dynamics with photon-starved techniques like XTA. In this paper, we demonstrate HRR-XMP and AXMP by measuring the laser-induced spectral dynamics of dilute aqueous solutions of Fe(CN)6 4- and [FeII(bpy)3]2+ (bpy: 2,2'-bipyridine), respectively.

Photochemical and Photophysical Dynamics of the Aqueous Ferrate(VI) Ion.

Ferrate(VI) has the potential to play a key role in future water supplies. Its salts have been suggested as "green" alternatives to current advanced oxidation and disinfection methods in water treatment, especially when combined with ultraviolet light to stimulate generation of highly oxidizing Fe(V) and Fe(IV) species. However, the nature of these intermediates, the mechanisms by which they form, and their roles in downstream oxidation reactions remain unclear. Here, we use a combination of optical and X-ray transient absorption spectroscopies to study the formation, interconversion, and relaxation of several excited-state and metastable high-valent iron species following excitation of aqueous potassium ferrate(VI) by ultraviolet and visible light. Branching from the initially populated ligand-to-metal charge transfer state into independent photophysical and photochemical pathways occurs within tens of picoseconds, with the quantum yield for the generation of reactive Fe(V) species determined by relative rates of the competing intersystem crossing and reverse electron transfer processes. Relaxation of the metal-centered states then occurs within 4 ns, while the formation of metastable Fe(V) species occurs in several steps with time constants of 250 ps and 300 ns. Results here improve the mechanistic understanding of the formation and fate of Fe(V) and Fe(IV), which will accelerate the development of novel advanced oxidation processes for water treatment applications.

Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency.

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.

Charge Carrier Screening in Photoexcited Epitaxial Semiconductor Nanorods Revealed by Transient X-ray Absorption Linear Dichroism.

Understanding the electronic structure and dynamics of semiconducting nanomaterials at the atomic level is crucial for the realization and optimization of devices in solar energy, catalysis, and optoelectronic applications. We report here on the use of ultrafast X-ray linear dichroism spectroscopy to monitor the carrier dynamics in epitaxial ZnO nanorods after band gap photoexcitation. By rigorously subtracting out thermal contributions and conducting ab initio calculations, we reveal an overall depletion of absorption cross sections in the transient X-ray spectra caused by photogenerated charge carriers screening the core-hole potential of the X-ray absorbing atom. At low laser excitation densities, we observe phase-space filling by excited electrons and holes separately. These results pave the way for carrier- and element-specific probing of charge transfer dynamics across heterostructured interfaces with ultrafast table-top and fourth-generation X-ray sources.

X-ray multi-probe data acquisition: A novel technique for laser pump x-ray transient absorption spectroscopy.

We report the development and implementation of a novel data acquisition (DAQ) technique for synchrotron-based laser pump X-ray Transient Absorption (XTA) spectroscopy, called X-ray Multi-Probe DAQ (XMP DAQ). This technique utilizes high performance analog to digital converters and home-built software to efficiently measure and process the XTA signal from all x-ray pulses between laser excitations. XMP DAQ generates a set of time resolved x-ray absorption spectra at thousands of different pump-probe time delays simultaneously. Two distinct XMP DAQ schemes are deployed to accommodate different synchrotron storage ring filling patterns. Current Integration (CI) DAQ is a quasi-analog technique that implements a fitting procedure to extract the time resolved absorption intensity from the averaged fluorescence detector response. The fitting procedure eliminates issues associated with small drifts in the voltage baseline and greatly enhances the accuracy of the technique. Photon Counting (PC) DAQ is a binary technique that uses a time resolved histogram to calculate the XTA spectrum. While PC DAQ is suited to measure XTA data with closely spaced x-ray pulses (∼10 ns) and a low count rate (<1 detected photon/pulse), CI DAQ works best for widely spaced pulses (tens of ns or greater) with a high count rate (>1 detected photon/pulse). XMP DAQ produces a two-dimensional XTA dataset, enabling efficient quantitative analysis of photophysical and photochemical processes from the sub-nanosecond timescale to 100 µs and longer.

Quantifying Photoinduced Polaronic Distortions in Inorganic Lead Halide Perovskite Nanocrystals.

The development of next-generation perovskite-based optoelectronic devices relies critically on the understanding of the interaction between charge carriers and the polar lattice in out-of-equilibrium conditions. While it has become increasingly evident for CsPbBr3 perovskites that the Pb-Br framework flexibility plays a key role in their light-activated functionality, the corresponding local structural rearrangement has not yet been unambiguously identified. In this work, we demonstrate that the photoinduced lattice changes in the system are due to a specific polaronic distortion, associated with the activation of a longitudinal optical phonon mode at 18 meV by electron-phonon coupling, and we quantify the associated structural changes with atomic-level precision. Key to this achievement is the combination of time-resolved and temperature-dependent studies at Br K and Pb L3 X-ray absorption edges with refined ab initio simulations, which fully account for the screened core-hole final state effects on the X-ray absorption spectra. From the temporal kinetics, we show that carrier recombination reversibly unlocks the structural deformation at both Br and Pb sites. The comparison with the temperature-dependent XAS results rules out thermal effects as the primary source of distortion of the Pb-Br bonding motif during photoexcitation. Our work provides a comprehensive description of the CsPbBr3 perovskites' photophysics, offering novel insights on the light-induced response of the system and its exceptional optoelectronic properties.

Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer.

It is well known that the solvent plays a critical role in ultrafast electron-transfer reactions. However, solvent reorganization occurs on multiple length scales, and selectively measuring short-range solute-solvent interactions at the atomic level with femtosecond time resolution remains a challenge. Here we report femtosecond X-ray scattering and emission measurements following photoinduced charge-transfer excitation in a mixed-valence bimetallic (FeiiRuiii) complex in water, and their interpretation using non-equilibrium molecular dynamics simulations. Combined experimental and computational analysis reveals that the charge-transfer excited state has a lifetime of 62 fs and that coherent translational motions of the first solvation shell are coupled to the back electron transfer. Our molecular dynamics simulations identify that the observed coherent translational motions arise from hydrogen bonding changes between the solute and nearby water molecules upon photoexcitation, and have an amplitude of tenths of ångströms, 120-200 cm-1 frequency and ~100 fs relaxation time. This study provides an atomistic view of coherent solvent reorganization mediating ultrafast intramolecular electron transfer.

Site-Selective Real-Time Observation of Bimolecular Electron Transfer in a Photocatalytic System Using L-Edge X-Ray Absorption Spectroscopy*.

Time-resolved X-ray absorption spectroscopy has been utilized to monitor the bimolecular electron transfer in a photocatalytic water splitting system. This has been possible by uniting the local probe and element specific character of X-ray transitions with insights from high-level ab initio calculations. The specific target has been a heteroleptic [IrIII (ppy)2 (bpy)]+ photosensitizer, in combination with triethylamine as a sacrificial reductant and Fe3(CO)12 as a water reduction catalyst. The relevant molecular transitions have been characterized via high-resolution Ir L-edge X-ray absorption spectroscopy on the picosecond time scale and restricted active space self-consistent field calculations. The presented methods and results will enhance our understanding of functionally relevant bimolecular electron transfer reactions and thus will pave the road to rational optimization of photocatalytic performance.

Micro-focused MHz pink beam for time-resolved X-ray emission spectroscopy.

The full radiation from the first harmonic of a synchrotron undulator (between 5 and 12 keV) at the Advanced Photon Source is microfocused using a stack of beryllium compound refractive lenses onto a fast-moving liquid jet and overlapped with a high-repetition-rate optical laser. This micro-focused geometry is used to perform efficient nonresonant X-ray emission spectroscopy on transient species using a dispersive spectrometer geometry. The overall usable flux achieved on target is above 1015 photons s-1 at 8 keV, enabling photoexcited systems in the liquid phase to be tracked with time resolutions from tens of picoseconds to microseconds, and using the full emission spectrum, including the weak valence-to-core signal that is sensitive to chemically relevant electronic properties.

Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity.

Ligand substitution reactions are common in solvated transition metal complexes, and harnessing them through initiation with light promises interesting practical applications, driving interest in new means of probing their mechanisms. Using a combination of time-resolved x-ray absorption spectroscopy and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations and x-ray absorption near-edge spectroscopy calculations, we elucidate the mechanism of photoaquation in the model system iron(ii) hexacyanide, where UV excitation results in the exchange of a CN- ligand with a water molecule from the solvent. We take advantage of the high flux and stability of synchrotron x-rays to capture high precision x-ray absorption spectra that allow us to overcome the usual limitation of the relatively long x-ray pulses and extract the spectrum of the short-lived intermediate pentacoordinated species. Additionally, we determine its lifetime to be 19 (±5) ps. The QM/MM simulations support our experimental findings and explain the ∼20 ps time scale for aquation as involving interconversion between the square pyramidal (SP) and trigonal bipyramidal pentacoordinated geometries, with aquation being only active in the SP configuration.

Energy Transfer from Antenna Ligand to Europium(III) Followed Using Ultrafast Optical and X-ray Spectroscopy.

A series of highly luminescent europium(III) complexes which exhibit photoluminescence from the Eu(III) center following energy transfer from the UV absorbing organic sensitizer have been investigated using a combination of ultrafast optical transient absorption and Eu L3 X-ray transient absorption techniques. We have previously demonstrated that the latter can be used as a signature of 4f-4f excitation responsible for the photoluminescence in these Eu(III) coordination complexes, but the long time scale of the earlier measurements did not allow direct observation of the ligand-to-metal energy transfer step, preventing a determination of the sensitization mechanism. Here, we provide the first direct experimental verification that Dexter electron exchange from the ligand triplet state is the dominant energy transfer mechanism in these photoluminescent systems. Moreover, the optical transient absorption results obtained herein imply that energy transfer for all three compounds has near unity yield, regardless of differences in the sensitization efficiencies, suggesting that the variations in the sensitization efficiencies are determined almost entirely by differences in the ligand-centered intersystem crossing rates. The implications for the rational design of more effective photoluminescent lanthanide complexes are discussed.

Using Ultrafast X-ray Spectroscopy To Address Questions in Ligand-Field Theory: The Excited State Spin and Structure of [Fe(dcpp)2]2.

We have employed a range of ultrafast X-ray spectroscopies in an effort to characterize the lowest energy excited state of [Fe(dcpp)2]2+ (where dcpp is 2,6-(dicarboxypyridyl)pyridine). This compound exhibits an unusually short excited-state lifetime for a low-spin Fe(II) polypyridyl complex of 270 ps in a room-temperature fluid solution, raising questions as to whether the ligand-field strength of dcpp had pushed this system beyond the 5T2/3T1 crossing point and stabilizing the latter as the lowest energy excited state. Kα and Kß X-ray emission spectroscopies have been used to unambiguously determine the quintet spin multiplicity of the long-lived excited state, thereby establishing the 5T2 state as the lowest energy excited state of this compound. Geometric changes associated with the photoinduced ligand-field state conversion have also been monitored with extended X-ray absorption fine structure. The data show the typical average Fe-ligand bond length elongation of ∼0.18 Å for a 5T2 state and suggest a high anisotropy of the primary coordination sphere around the metal center in the excited 5T2 state, in stark contrast to the nearly perfect octahedral symmetry that characterizes the low-spin 1A1 ground state structure. This study illustrates how the application of time-resolved X-ray techniques can provide insights into the electronic structures of molecules-in particular, transition metal complexes-that are difficult if not impossible to obtain by other means.

Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths.

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.

Revealing hole trapping in zinc oxide nanoparticles by time-resolved X-ray spectroscopy.

Nanostructures of transition metal oxides, such as zinc oxide, have attracted considerable interest for solar-energy conversion and photocatalysis. Both applications are sensitive to the transport and trapping of photoexcited charge carriers. The probing of electron trapping has recently become possible using time-resolved element-sensitive methods, such as X-ray spectroscopy. However, valence-band-trapped holes have so far escaped observation. Herein we use X-ray absorption spectroscopy combined with a dispersive X-ray emission spectrometer to probe the charge carrier relaxation and trapping processes in zinc oxide nanoparticles after above band-gap photoexcitation. Our results, supported by simulations, demonstrate that within 80 ps, photoexcited holes are trapped at singly charged oxygen vacancies, which causes an outward displacement by ~15% of the four surrounding zinc atoms away from the doubly charged vacancy. This identification of the hole traps provides insight for future developments of transition metal oxide-based nanodevices.

Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy.

We probe the dynamics of valence electrons in photoexcited [Fe(terpy)2]2+ in solution to gain deeper insight into the Fe-ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making it a powerful technique for molecular studies in a wide variety of environments. A picosecond-time-resolved measurement of the complete 1s X-ray emission spectrum captures the transient photoinduced changes and includes the weak valence-to-core (vtc) emission lines that correspond to transitions from occupied valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitals directly involved in the light-driven dynamics; a change in the metal-ligand orbital overlap results in an intensity reduction and a blue energy shift in agreement with our theoretical calculations and more subtle features at the highest energies reflect changes in the frontier orbital populations.

Tracking the Structural and Electronic Configurations of a Cobalt Proton Reduction Catalyst in Water.

X-ray transient absorption spectroscopy (X-TAS) has been used to study the light-induced hydrogen evolution reaction catalyzed by a tetradentate macrocyclic cobalt complex with the formula [LCo(III)Cl2](+) (L = macrocyclic ligand), [Ru(bpy)3](2+) photosensitizer, and an equimolar mixture of sodium ascorbate/ascorbic acid electron donor in pure water. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis of a binary mixture of the octahedral Co(III) precatalyst and [Ru(bpy)3](2+) after illumination revealed in situ formation of a Co(II) intermediate with significantly distorted geometry and electron-transfer kinetics of 51 ns. On the other hand, X-TAS experiments of the complete photocatalytic system in the presence of the electron donor showed the formation of a square planar Co(I) intermediate species within a few nanoseconds, followed by its decay in the microsecond time scale. The Co(I) structural assignment is supported by calculations based on density functional theory (DFT). At longer reaction times, we observe the formation of the initial Co(III) species concomitant to the decay of Co(I), thus closing the catalytic cycle. The experimental X-ray absorption spectra of the molecular species formed along the catalytic cycle are modeled using a combination of molecular orbital DFT calculations (DFT-MO) and finite difference method (FDM). These findings allowed us to assign the full mechanistic pathway, followed by the catalyst as well as to determine the rate-limiting step of the process, which consists in the protonation of the Co(I) species. This study provides a complete kinetics scheme for the hydrogen evolution reaction by a cobalt catalyst, revealing unique information for the development of better catalysts for the reductive side of hydrogen fuel cells.

Feasibility of Valence-to-Core X-ray Emission Spectroscopy for Tracking Transient Species.

X-ray spectroscopies, when combined in laser-pump, X-ray-probe measurement schemes, can be powerful tools for tracking the electronic and geometric structural changes that occur during the course of a photoinitiated chemical reaction. X-ray absorption spectroscopy (XAS) is considered an established technique for such measurements, and X-ray emission spectroscopy (XES) of the strongest core-to-core emission lines (Kα and Kß) is now being utilized. Flux demanding valence-to-core XES promises to be an important addition to the time-resolved spectroscopic toolkit. In this paper we present measurements and density functional theory calculations on laser-excited, solution-phase ferrocyanide that demonstrate the feasibility of valence-to-core XES for time-resolved experiments. We discuss technical improvements that will make valence-to-core XES a practical pump-probe technique.