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At least 1,009 records · Page 56

In situ irradiation of spent nuclear fuels

To improve the economics of commercial nuclear reactors, nuclear vendors and utilities are seeking approval for increased burnup usage of the existing nuclear fleet. This is especially critical for meeting the clean energy initiative by the United States Government, Department of Energy (DOE). However, one of the key challenges the nuclear industry faces in this regard is that the regions exposed to high burnup and low temperatures exhibit a fine-grained microstructure with large bubbles known as high-burnup structure (HBS) [1]. The formation of HBS has been correlated to the diminished performance of the reactor, as well as fuel fragmentation and pulverization during transient and accidental conditions [2]. Therefore, it is paramount to understand the mechanisms for HBS formation along with its impact on the properties and performance of nuclear fuels. While existing programs, such as Nuclear Energy Advanced Modeling and Simulation (NEAMS) and Advanced Fuel Campaign (AFC) are focusing on evaluating the performance impact of HBS, the physical mechanisms contributing to HBS formation are still not fully understood. In addition, having predictive capabilities and sound understanding of the microstructural evolution of nuclear fuel is essential for accelerated development, qualification, and deployment of new nuclear materials and novel reactor designs for advanced nuclear reactors. There is a lack of consensus among researchers regarding the mechanisms leading to such restructuring observed in HBS. Grain subdivision due to polygonization versus recrystallization, continuous versus discrete recrystallization occurring in tandem or conjunction, etc., have been proposed and debated. In general, it is hypothesized that defect accumulation and dislocation interaction within the grains cause the realignment of dislocations into grain boundaries, leading to the new subgrain formation, which over time transforms into new grains. However, due to the lack of transient data, the importance of fission rate, irradiation, thermal, and stress history of the fuel on the restructuring could not be assessed. In situ microstructural evolution under various irradiation conditions is desired to bridge this gap. Alternatively, phase-field-based models have been developed to capture HBS formation via discrete recrystallization utilizing the classical nucleation approach [3–5]. However, in these models, the grain nucleation criteria are often defined based on empirical relations for burnup and fission gas density leading to dislocation density change. A mechanistic approach to capture the dislocation interaction with the microstructural features leading to grain subdivision is lacking.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Attosecond Time-Domain Measurement of Core-Level-Exciton Decay in Magnesium Oxide

Excitation of ionic solids with extreme ultraviolet pulses creates localized core-level excitons, which in some cases couple strongly to the lattice. In this paper, core-level-exciton states of magnesium oxide are studied in the time domain at the Mg L 2 , 3 edge with attosecond transient reflectivity spectroscopy. Attosecond pulses trigger the excitation of these short-lived quasiparticles, whose decay is perturbed by time-delayed near-infrared pulses. Combined with a few-state theoretical model, this reveals that the infrared pulse shifts the energy of bright (dipole-allowed) core-level-exciton states as well as induces features arising from dark core-level excitons. We report coherence lifetimes for the two lowest core-level excitons of 2.3 ± 0.2 and 1.6 ± 0.5 fs and show that these are primarily a consequence of strong exciton-phonon coupling, disclosing the drastic influence of structural effects in this ultrafast relaxation process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Atomistic Origin of Microsecond Carrier Lifetimes at Perovskite Grain Boundaries: Machine Learning-Assisted Nonadiabatic Molecular Dynamics

The polycrystalline nature of perovskites, stemming from their facile solution-based fabrication, leads to a high density of grain boundaries (GBs) and point defects. However, the impact of GBs on perovskite performance remains uncertain, with contradictory statements found in the literature. We developed a machine learning force field, sampled GB structures on a nanosecond time scale, and performed nonadiabatic (NA) molecular dynamics simulations of charge carrier trapping and recombination in stoichiometric and doped GBs. The simulations reveal long, microsecond carrier lifetimes, approaching experimental data, stemming from charge separation at the GBs and small NA coupling, 0.01–0.1 meV. Stoichiometric GBs exhibit transient trap states, which, however, are not particularly detrimental to the carrier lifetime. Halide dopants form interstitial defects in the bulk, but have a stabilizing influence on the GB structure by passivating undersaturated Pb atoms and reducing the transient trap state formation. On the contrary, excess Pb destabilizes GBs, allowing formation of persistent midgap states that trap charges. Still, the charge carrier lifetime reduces relatively little, because the midgap states decouple from the bands, and charges are more likely to escape back into bands upon a GB structural fluctuation. The atomistic study into the structural dynamics of perovskite GBs and its influence on charge carrier trapping and recombination provides valuable insights into the complex properties of perovskites and the intricate role of GBs in the material performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design considerations for optimizing the transient CHI injector on QUEST

Transient coaxial helicity injection (transient CHI) on the QUEST (Q-shu University Experiment with Steady-State ST) spherical tokamak (ST) has recently validated the floating biased electrode configuration for solenoid-free plasma startup. In support of a significant divertor upgrade on QUEST, the details of the transient CHI injector geometry on QUEST have been examined more closely using tokamak simulation code (TSC) simulations. QUEST uses a HIT-II-like (Helicity Injected Torus) injector configuration in which the injector region is comprised of coaxial injector electrodes located in the lower part of the machine. TSC simulations indicate high injector flux operation may benefit from an increased gap between the coaxial electrodes. This is the first study to examine the differences between an open and closed electrode configuration for solenoid-free plasma startup using transient CHI. Results show that both configurations can generate similar levels of closed flux, but the closed configuration may be easier to implement in some ST designs as a much smaller portion of the injector needs to be close to the injector flux coil. Results show that increasing the electrode gap width from the present 10.8 cm to about 15–20 cm would increase the closed flux fraction by about 40%. The results presented in this paper are generally applicable to the CHI design for other STs.

coaxial helicity injection↗

Defect-Limited Mobility and Defect Thermochemistry in Mixed A-Cation Tin Perovskites: (CH3NH3)1-xCsxSnBr3

Hybrid organic-inorganic semiconductors crystallizing in the perovskite structure present a significant opportunity for realizing defect-tolerant semiconductors. In this work, we examine the solid solution, (CH3NH3)1-xCsxSnBr3, and identify the thermochemistry dictating the intrinsic carrier concentrations and how local structural distortions influences this electronic behavior. This family of compounds exhibits the expected systematic trend in decreasing optical gap with the cesium to methylammonium A-site mixing ratio, x, in the visible region. However, the carrier mobility, as determined from time-resolved microwave conductivity measurements, trends opposite to that expected from first-principles calculations combined with Boltzmann scattering theory calculations of the carrier mobility. We propose that this is a result of increasing carrier scattering with x in (CH3NH3)1-xCsxSnBr3 due to a significant increase in the carrier density with x. By examining the dependence of the carrier density as a function of x, we infer the compositional-dependence of the average enthalpy and nonconfigurational entropy per defect. While diffraction reveals a cubic aristotypic perovskite structure as a function of x at room temperature, the pair distribution functions obtained from synchrotron X-ray total scattering from these materials are better described by symmetry-adapted displacement modes of the Pm3m crystal structure, which we attribute to a large degree of anharmonic dynamics of the atom positions. This analysis shows that CH3NH3+-rich compositions retain mostly linear Sn-Br-Sn bonding environments through the displacements, while Cs+-rich compositions lead to more significantly bent Sn-Br-Sn environments. We propose that these bent bonding arrangements in Cs-rich compositions yield a higher propensity for defect formation. This also provides a rationale for carrier trapping that gives rise to anomalous microwave transients. Together, these results provide insight into the structure-dynamics-properties relationships in this highly anharmonic system with high amplitude atomic motions and low defect formation energies.

defect thermochemistry↗

SlimIO: Lightweight I/O Path Design for Write Isolation in FDP-backed In-Memory Databases

In-Memory Databases (IMDBs) are widely used with HPC applications to manage transient data, often using snapshot-based persistence for backups. Redis, a representative IMDB, employs both snapshot and Write-Ahead Log (WAL) mechanisms, storing data on persistent devices via the traditional kernel I/O path. This method incurs syscall overhead, I/O contention between processes, and SSD garbage collection (GC) delays. To address these issues, we propose SlimIO, which adopts I/O passthru to minimize syscall overhead and inter-process I/O interference. Additionally, it leverages Flexible Data Placement (FDP) SSDs as backup storage to avoid performance degradation from SSD GC. Experimental results show that SlimIO reduces snapshot time by up to 25%, increases query throughput by up to 30% during non-snapshot periods, and lowers 99.9%-ile latency by up to 50%. Furthermore, it achieves a write amplification factor (WAF) of 1.00, indicating no redundant internal writes, thus extending SSD lifespan.

Lee, Sangyun [Sogang University]↗

An asymmetric electron-scattering photosphere around optical tidal disruption events

We report a star crossing the tidal radius of a supermassive black hole will be spectacularly ripped apart with an accompanying burst of radiation. A few tens of such tidal disruption events have now been identified in optical wavelengths, but the exact origin of the strong optical emission remains inconclusive. Here we report polarimetric observations of three tidal disruption events. The continuum polarization appears independent of wavelength, while emission lines are partially depolarized. These signatures are consistent with photons being scattered and polarized in an envelope of free electrons. An almost axisymmetric photosphere viewed from different angles is in broad agreement with the data, but there is also evidence for deviations from axial symmetry before the peak of the flare and significant time evolution at early times, compatible with the rapid formation of an accretion disk. By combining a super-Eddington accretion model with a radiative transfer code, we simulate the polarization degree as a function of disk mass and viewing angle and we show that the predicted levels are compatible with the observations for extended reprocessing envelopes of ~1,000 gravitational radii. Spectropolarimetry therefore constitutes a new observational test for tidal disruption event models, and opens an important new line of exploration in the study of tidal disruption events.

79 ASTRONOMY AND ASTROPHYSICS↗

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. Here 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen Bonding Optimizes Singlet Fission in Carboxylic Acid Functionalized Anthradithiophene Films

The rate of singlet fission, the process of generating two triplet excitons with photoexcitation of one singlet exciton, depends on a combination of singlet/triplet energy balance and intermolecular coupling. In this work, we perform carboxylic acid functionalization of anthradithiophene (ADT) derivatives that result in hydrogen bonds that drive molecular orientation and strong electronic coupling of polycrystalline ADT thin films, leading to ultrafast singlet fission without significant enthalpic driving force. ADT with a single carboxylic acid group exhibits weak intermolecular coupling and slow and inefficient singlet fission, much like the parent ADT, and substitution of different alkylsilyl solubilizing groups has little effect. However, the addition of two carboxylic acid groups on either end of the long axis favors significant coupling and crystallinity in as-deposited thin films that increase the effective singlet fission rate by roughly three orders of magnitude. The properties of the triplet pair, particularly its propensity to form long-lived independent triplets, are also influenced by the degree of long-range intermolecular coupling. The enhancement of intermolecular coupling specific to singlet fission using the ubiquitous cyclic hydrogen bonding motif could impact triplet pair utilization schemes in a variety of contexts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catching the Killer: Dynamic Disorder Design Rules for Small–Molecule Organic Semiconductors

Small-molecule organic semiconductors are promising materials for applications ranging from solar cells to medical sensors. Their nearly infinite design space means that, in theory, it is possible to tailor the material to the exact specifications of a particular application. In reality; however, design rules to improve mobility (μ) remain elusive because of the complex calculations required to understand its limiters. Transient localization theory posits that charge carriers are slowed down by the collective phonon motions, called dynamic disorder, which localize charge carriers temporarily. Traditionally, a mode-by-mode analysis is performed to try and identify “killer” modes. Herein, the flaws are demonstrated with this analysis and present a streamlined simulation workflow that simplifies simulation of dynamic disorder and enables engineering of new molecular structures based on phonon dynamics. This workflow is combined with a novel visualization technique that enables per-atom insights into how μ is limited. Furthermore, this workflow is applied and analyzed to a series of -acenes and a series of BTBT-based molecules. Then design rules are identified in each series that identify possible ways to improve the μ beyond current experimental limits using phonon engineering.

36 MATERIALS SCIENCE↗

Janus Monolayers for Ultrafast and Directional Charge Transfer in Transition Metal Dichalcogenide Heterostructures

Charge transfer properties of van der Waals heterostructures formed by Janus and regular transition metal dichalcogenide monolayers are studied by time-resolved pump–probe measurements and photoluminescence spectroscopy. Measurements of electron and hole transfer in three heterostructures with atomic layer sequences of S–W–Se/S–W–S, Se–W–S/S–W–S, and S–W–Se/Se–W–Se reveal that charge transfer from regular to Janus monolayers is ultrafast regardless of the direction of the built-in electric field of the Janus monolayer (Janus field). However, the charge transfer from Janus to regular layers is directional and controlled by the Janus field. When the current direction is along the field, the charge transfer is ultrafast and efficient, while the field blocks the charge transfer with an opposite charge current direction. The transferred carriers form interlayer excitons with extended lifetimes compared to the intralayer excitons. The demonstrated ultrafast and directional charge transfer between Janus and regular TMD layers shows that the Janus structures can be used to make 2D heterostructures with efficient and directional charge transfer properties.

36 MATERIALS SCIENCE↗

Origin of proton irradiation-induced deep acceptors in Al 0.70 Ga 0.30 N

Deep level defect introduction and carrier removal were characterized using steady-state photocapacitance (SSPC), deep level transient spectroscopy (DLTS) and lighted capacitance–voltage for proton irradiated n-type Al 0.70 Ga 0.30 N Schottky diodes grown by metal-organic vapor phase epitaxy on AlN-on-sapphire templates. SSPC observed deep levels in the as-grown diode with zero-phonon transition energies of 2.20, 2.65, 3.10, 3.40, and 4.65 eV relative to the conduction band minimum (E c ), and an additional deep level emerged at 1.20 eV with irradiation. Lighted capacitance–voltage measurements quantified the deep level concentration (N t ) of states detected by SSPC, and it was observed that N t increased with proton fluence only for the 1.2 and 4.65 eV levels. Carrier removal was much larger than the increase in N t of the 1.2 and 4.65 eV deep levels, suggesting that radiation-induced deep level compensators existed beyond what was detected with SSPC. DLTS detected additional, proton-induced deep acceptors at E c —0.55, 0.82, and 1.16 eV, the latter of which is likely the same 1.20 eV deep state observed by SSPC. The concentration of the E c —0.82 eV defect state was large enough to reconcile carrier removal with total deep level introduction. Comparing the E c —0.82 and 1.16 eV deep acceptor levels to previous experimental and theoretical reports suggests that their atomistic origins could be the nitrogen vacancy (V N ) and oxygen substituting on the nitrogen sub-lattice (O N ), respectively. This defect behavior contrasts starkly with GaN, where V N and O N are shallow donors, and demonstrates that the electronic properties of defects can evolve drastically within the AlGaN alloy system ranging from wide bandgap GaN to ultra-wide bandgap AlN.

Armstrong, Andrew Michael [Sandia National Laborat↗

Resolving femtosecond photoinduced energy flow: capture of nonadiabatic reaction pathway topography and wavepacket dynamics from photoexcitation through the conical intersection seam (Final Technical Report)

The dynamics that take place within just tens to hundreds of femtoseconds following the absorption of light by a molecule can play a critical role in how the absorbed energy is directed, allowing it to be used for a specific function or dissipated harmlessly. The form of chemical change that occurs rapidly in these molecules is called a “nonadiabatic electronic transition.” Such transitions are known to mediate energy flow in natural biological systems such as the ultraviolet photoprotection mechanism of DNA and the first step of the human vision response. Understanding how these mechanisms work precisely may help scientists achieve controlled manipulation of solar energy or optical control of a wide range of energy management functions in artificial systems. Experimental methods, however, have not yet allowed a precisely resolved and complete measurement of nonadiabatic electronic transitions. This constitutes a major obstacle to progress in the field. For progress to occur that would inform a wide body of research aiming to efficiently harness the energy of light for practical purposes, it is especially important to benchmark computational models of the molecules undergoing these rapid changes with experimental measurements, in order to learn which models are accurate. With Dept. of Energy funding, we have made strong progress towards establishing a new optical method for experimentally detecting the full nonadiabatic electronic transition. This requires having coordinated pulses of light covering the visible through the mid-infrared range of the electromagnetic spectrum that last only ten femtoseconds. We have developed a new, relatively simple approach for generating such pulses of laser light, and have incorporated them into a time-resolved spectrometer for measuring rapid changes in molecules. These tools can provide the greater precision and new types of data that are needed to benchmark computational models of molecular change and thus to make progress in the field. Our tools were tested on graphene, an excellent solid-state sample for verifying the capabilities and limitations of our instrumentation. The investment made in these tools by the Dept. of Energy Office of Science will allow new fundamental scientific understanding of energy dynamics in molecules in future studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generation of excited species in a streamer discharge

At or near atmospheric pressure, most transient discharges, particularly in molecular gases or gas mixture containing molecular gases result in a space-charge dominated transport called a streamer discharge. The excited species generation in such discharges forms the basis for plasma chemistry in most technological applications. In this paper we simulate the propagation of streamers in atmospheric pressure N 2 to understand the energy partitioning in the formation of various excited species and compare the results to a uniform Townsend discharge. The model is fully two-dimensional with azimuthal symmetry. Results show a significantly larger fraction of the energy goes into vibrational excitation of the N 2 ground state in a streamer-type discharge in comparison to a Townsend discharge. For lower applied voltages, the anode-directed (negative) steamer is slightly more efficient in channeling energy for excited species production in comparison to a cathode-directed (positive) streamer. Near 70% overvoltage both types of streamers show very similar energy partitioning but quite different from a Townsend discharge.

42 ENGINEERING↗

Recent Developments in Revealing the Impact of Complex Metal Oxide Reconstruction on Catalysis

Surface reconstruction of complex metal oxides refers to the alterations of the topmost catalyst surface, relative to the bulk structure, following exposure to pretreatment or reaction conditions during heterogeneous catalysis. (1) This structural and electronic transformation may involve (1) changes of the exposed crystallographic facets, (2) changes in chemical composition, such as the enrichment of specific elements, and, (3) morphological variations, including surface roughness and defects (Scheme 1). Beyond relaxation, surface reconstruction here also encompasses disruptions to the periodicity of the sublayers and changes to its stoichiometry. This change significantly influences the chemical properties of the catalyst surface, such as redox sites, (2) acid/base pairs, hydroxyl groups, (3) and surface defects. Surface reconstruction occurs due to the thermodynamic drive to lower the surface energy of the catalyst under the surrounding environment (e.g., temperature, chemical potential of species present). In addition to the treatment or reaction conditions, the extent of reconstruction also depends on the elements in the metal oxide structure. For instance, annealing ABO 3 perovskites (SrTiO 3 , BaTiO 3 , and BaZrO 3 ) at high temperatures (500 °C) in O 2 has a very different impact on the A/B ratio at the surface (ranging from 0.9 to 2.5), depending on the identity of A and B. (4) Metal oxide surface reconstruction under an electric field and exposure to acidic and alkaline media has recently gained increased attention in electrocatalysis, such as in the oxygen evolution reaction (OER); (5,6) however, in this Viewpoint we focus on the impact of surface reconstruction on thermal catalysis, a critical enduring research theme with ongoing challenges. Here, we start showcasing approaches to characterize surface reconstruction at the topmost surface layer, such as low-energy ion scattering (LEIS), discussing advantages and limitations. Next, we connect characterization of surface reconstruction to site-specific kinetic analysis, enabled via steady-state isotopic transient kinetic analysis (SSITKA), and we express our viewpoint on building structure–performance relationships by deeply understanding reconstructed surfaces. Later, we comment on the potential of tuning surface reconstruction to enhance catalytic performance. Finally, we explore the interplay between surface reconstruction and the “intelligent behavior”.

alcohol conversion↗

Impact of Actinide Complexation on Ligand Radiolysis

Although the actinides boast many unique physical and chemical properties, their inherent susceptibility to radioactive decay are what make them truly interesting elements to study. The absorption of ionizing radiation from actinide decay leads to the formation of a variety of transient and steady-state radicals, ions, and molecular radiolysis products that can lead to significant changes in the surrounding environment, and ultimately dictate steady-state actinide redox distributions and the longevity of molecules designed for actinide complexation. Radiolysis of the latter leads to complexant destruction and the concomitant formation of degradation products that can complicate actinide studies and processes. However, the radiation chemistry of most actinide complexants have been studied in the absence of the actinides they were designed to complex, which can lead to inaccurate conclusions on longevity and degradation product distributions, as metal ion complexation has been historically shown to influence a ligand’s radiolytic behavior. Consequently, bridging this knowledge gap is important for actinide science. Here, I will discuss the impact of actinide complexation on the steady-state and time-resolved radiation-induced reactivity of a variety of complexants, including, tributyl phosphate (TBP) and N,N,N',N'-tetraoctyl diglycolamide (TODGA) .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Visible-Light-Driven, Iridium-Catalyzed Hydrogen Atom Transfer: Mechanistic Studies, Identification of Intermediates, and Catalyst Improvements

The harvesting of visible light is a powerful strategy for the synthesis of weak chemical bonds involving hydrogen that are below the thermodynamic threshold for spontaneous H 2 evolution. Piano-stool iridium hydride complexes are effective for the bluelight- driven hydrogenation of organic substrates and contrathermodynamic dearomative isomerization. In this work, a combination of spectroscopic measurements, isotopic labeling, structure–reactivity relationships, and computational studies has been used to explore the mechanism of these stoichiometric and catalytic reactions. Photophysical measurements on the iridium hydride catalysts demonstrated the generation of long-lived excited states with principally metal-to-ligand charge transfer (MLCT) character. Transient absorption spectroscopic studies with a representative substrate, anthracene revealed a diffusion-controlled dynamic quenching of the MLCT state. The triplet state of anthracene was detected immediately after the quenching events, suggesting that triplet–triplet energy transfer initiated the photocatalytic process. The key role of triplet anthracene on the post-energy transfer step was further demonstrated by employing photocatalytic hydrogenation with a triplet photosensitizer and a HAT agent, hydroquinone. DFT calculations support a concerted hydrogen atom transfer mechanism in lieu of stepwise electron/proton or proton/electron transfer pathways. Kinetic monitoring of the deactivation channel established an inverse kinetic isotope effect, supporting reversible C(sp 2 )–H reductive coupling followed by rate-limiting ligand dissociation. Mechanistic insights enabled design of a piano-stool iridium hydride catalyst with a rationally modified supporting ligand that exhibited improved photostability under blue light irradiation. The complex also provided improved catalytic performance toward photoinduced hydrogenation with H 2 and contra-thermodynamic isomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ferricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy

Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kβ main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kβ main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗