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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

M-Edge Spectroscopy of Transition Metals: Principles, Advances, and Applications

M-edge X-ray absorption spectroscopy (XAS), which probes 3p→3d transitions in first-row transition metals, provides detailed insights into oxidation states, spin-states, and local electronic structure with high element and orbital specificity. Operating in the extreme ultraviolet (XUV) region, this technique provides sharp multiplet-resolved features with high sensitivity to ligand field and covalency effects. Compared to K- and L-edge XAS, M-edge spectra exhibit significantly narrower full widths at half maximum (typically 0.3–0.5 eV versus >1 eV at the L-edge and >1.5–2 eV at the K-edge), owing to longer 3p core-hole lifetimes. M-edge measurements are also more surface-sensitive due to the lower photon energy range, making them particularly well-suited for probing thin films, interfaces, and surface-bound species. The advent of tabletop high-harmonic generation (HHG) sources has enabled femtosecond time-resolved M-edge measurements, allowing direct observation of ultrafast photoinduced processes such as charge transfer and spin crossover dynamics. This review presents an overview of the fundamental principles, experimental advances, and current theoretical approaches for interpreting M-edge spectra. We further discuss a range of applications in catalysis, materials science, and coordination chemistry, highlighting the technique’s growing impact and potential for future studies.

M-edge XANES↗
DOE OSTI2025

Factors Controlling Electrochemistry-Induced Deposition of a Zeolitic Imidazolate Framework-8 Film on Underlying Substrates

This paper discusses factors controlling electrochemistry-induced deposition of a zeolitic imidazolate framework-8 (ZIF-8) film on a planar substrate that is placed under an electrode. This method, which was recently demonstrated by us [T. Ito, et al. Cryst. Growth Des., 23, 6369 (2023)], provides a simple means to form a ZIF-8 film having lateral dimensions replicating those of a working electrode on an underlying substrate. We reported the effects of applied cathodic potential, electrode–substrate distance, and deposition time on the film formation, and proposed a mechanism involving cathodic base generation at a working electrode that promoted ligand deprotonation to form intermediate species, followed by their diffusion toward an underlying substrate. Here, we discuss details on the deposition mechanism by investigating the influences of other factors on the film deposition. We have investigated the effects of precursor concentration on film formation, and clarified that O 2 is a probase, rather than H 2 O. We have also shown the influences of substrate surface properties controlled by self-assembled monolayers on film thickness and morphology. Most notably, we successfully demonstrated the formation of microscale ZIF-8 films using an ultramicroelectrode, revealing the applicability of the electrochemistry-induced method for micropatterned film deposition on an underlying substrate.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Microscale Thermophoresis (MST) as a Tool to Study Binding Interactions of Oxygen-Sensitive Biohybrids

Microscale thermophoresis (MST) is a technique used to measure the strength of molecular interactions. MST is a thermophoretic-based technique that monitors the change in fluorescence associated with the movement of fluorescent-labeled molecules in response to a temperature gradient triggered by an IR LASER. MST has advantages over other approaches for examining molecular interactions, such as isothermal titration calorimetry, nuclear magnetic resonance, biolayer interferometry, and surface plasmon resonance, requiring a small sample size that does not need to be immobilized and a high-sensitivity fluorescence detection. In addition, since the approach involves the loading of samples into capillaries that can be easily sealed, it can be adapted to analyze oxygen-sensitive samples. In this Bio-protocol, we describe the troubleshooting and optimization we have done to enable the use of MST to examine protein–protein interactions, protein–ligand interactions, and protein–nanocrystal interactions. The salient elements in the developed procedures include 1) loading and sealing capabilities in an anaerobic chamber for analysis using a NanoTemper MST located on the benchtop in air, 2) identification of the optimal reducing agents compatible with data acquisition with effective protection against trace oxygen, and 3) the optimization of data acquisition and analysis procedures. The procedures lay the groundwork to define the determinants of molecular interactions in these technically demanding systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Quantum Mechanical Simulations of Dynamics of Electronic Excitations in Low-Dimensional Photovoltaics Materials

Dynamics of electronically excited states including exciton generation and relaxation, exciton-exciton interaction, and charge/energy transfer and transport, are critical to understanding and optimizing photovoltaic materials. Although considerable progress has been made, accurate experimental characterization of such crucial dynamics remains extremely challenging, especially in low-dimensional materials. In this talk, I will discuss how the advancement of quantum mechanical simulations of the dynamics of electronic excitations can reveal the physical mechanisms hindering or improving solar energy harvest. Specifically, we find that surface dangling-bond defects on silicon quantum dots cause rapid charge recombination and low carrier mobility in the inorganic-organic PV cells. Although small quantum dots are essentially free of defects, their optical gaps are too large. To solve this issue, a full-spectrum-light-absorption scheme is computationally designed, taking advantage of complexity and flexibility of low-dimensional materials consisting of different characteristics and dimensions. In this scheme the multifunctional ligands are used to (1) passivate against oxidation, (2) facilitate interfacial charge transfer, and (3) improve both charge transport and optical absorption. A joint theoretical and experimental study has demonstrated the feasibility of this approach. Finally, I will briefly talk about how this scheme and the well-tested quantum mechanical simulations can be employed to help improve energy-conversion efficiency in perovskite photovoltaics including perovskite-based tandem cells.

Zhigang Wu↗
DOE OSTI2024

Signatures of polarized chiral spin disproportionation in rare earth nickelates

In rare earth nickelates (RENiO 3 ), electron-lattice coupling drives a concurrent metal-to-insulator and bond disproportionation phase transition whose microscopic origin has long been the subject of active debate. Of several proposed mechanisms, here we test the hypothesis that pairs of self-doped ligand holes spatially condense to provide local spin moments that are antiferromagnetically coupled to Ni spins. These singlet-like states provide a basis for long-range bond and spiral spin order. Using magnetic resonant X-ray scattering on NdNiO 3 thin films, we observe the chiral nature of the spin disproportionated state, with spin spirals propagating along the crystallographic (101) ortho direction. These spin spirals are found to preferentially couple to X-ray helicity, establishing the presence of a hitherto-unobserved macroscopic chirality. The presence of this chiral magnetic configuration suggests a potential multiferroic coupling between the noncollinear magnetic arrangement and improper ferroelectric behavior as observed in prior studies on NdNiO 3 (101) ortho films and RENiO 3 single crystals. Experimentally constrained theoretical double-cluster calculations confirm the presence of an energetically stable spin-disproportionated state with Zhang-Rice singlet-like combinations of Ni and ligand moments

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS2005

Skeletal phenotype of growing transgenic mice that express a function-perturbing form of beta1 integrin in osteoblasts

Skeletal modeling entails the deposition of large amounts of extracellular matrix (ECM) to form structures tailored to withstand increasing mechanical loads during rapid growth. Specific ECM molecules bind to integrin receptors on the cell surface, thereby triggering a cascade of signaling events that affect critical cell functions. To evaluate the role of integrins during skeletal growth, transgenic mice were engineered to express a function-perturbing fragment of beta1 integrin consisting of the transmembrane domain and cytoplasmic tail under the control of the osteocalcin promoter (TG mice). Thus, transgene expression was targeted to mature cells of the osteoblast lineage, and herein we show that cultured cells resembling osteocytes from 90-day-old TG mice display impaired adhesion to collagen I, a ligand for beta1 integrin. To determine the influence of beta1 integrin on bones that are responsible for providing structural support during periods of rapid growth, we examined the phenotype of the appendicular skeleton in TG mice compared to wild type (WT) mice. According to radiographs, bones from mice of both genotypes between 14 and 90 days of age appeared similar in gross structure and density, although proximal tibiae from 35-90 days old TG mice were less curved than those of WT mice (72-92% TG/WT). Although there were only mild and transient differences in absolute bone mass and strength, once normalized to body mass, the tibial dry mass (79.1% TG/WT females), ash mass (78.5% TG/WT females), and femoral strength in torsion (71.6% TG/WT females) were reduced in TG mice compared to WT mice at 90 days of age. Similar effects of genotype on bone mass and curvature were observed in 1-year-old retired breeders, indicating that these phenotypic differences between TG and WT mice were stable well into adulthood. Effects of genotype on histomorphometric indices of cancellous bone turnover were minimal and evident only transiently during growth, but when present they demonstrated differences in osteoblast rather than osteoclast parameters. Together, these results suggest that integrin signals generated during growth enhance the acquisition of a skeletal mass, structure, and strength to withstand the mechanical loads generated by weight-bearing.

Antigens, CD29/genetics/metabolism↗
DOE OSTI2025

Determining the Conformation of Supported Complexes Using an 17 O TEDOR-like NMR Experiment

Dynamic nuclear polarization surface-enhanced nuclear magnetic resonance (NMR) spectroscopy has enabled the determination of the three-dimensional configuration of surface sites, in particular supported metal complexes of relevance to single-site heterogeneous catalysis. These approaches have chiefly leveraged the application of NMR double-resonance experiments that either reveal the complex conformation via point-to-point intramolecular distances between spin-labeled atoms or the complex-surface orientation via distances between the spins and the surface plane. Either method typically requires expensive isotope labeling and each reports on different structural features. The application of an experiment that simultaneously reveals both types of distances with chemical resolution would be ideal. Here, in this article, we describe an 17 O{ 1 H} pseudo-3D correlation experiment that achieves this goal. Specifically, Si–O–Si and Si–O–M oxygens are well-resolved by 17 O NMR; therefore, distances can be simultaneously measured radially, between Si– 17 O–M and the 1 H’s of the ligands, and vertically to the Si– 17 O–Si linkages of the silica support. We demonstrate the experiment using supported yttrium and zirconium complexes. Good agreement is obtained when comparing the experimental results to theoretical predictions from density functional theory calculations, highlighting the reliability of this relatively simple experiment.

alkyls↗
DOE OSTI2025

Directed Synthesis of Gold Nanoparticle Superstructures Using Self-Assembling Peptoids Containing Metal-Bonding N-Heterocyclic Carbenes

N-Heterocyclic carbene (NHC) ligands, with strong metal-binding affinity, offer a robust platform for constructing organic–inorganic nanohybrids with high stability and tunable properties. However, achieving precise structural control in a simple manner remains challenging. Here, we report a one-pot synthesis of nanohybrids using self-assembling peptoids functionalized with histidine-2-ylidene, which simultaneously enable peptoid assembly and NHC–metal binding. Histidine-2-ylidene-functionalized peptoids were designed to self-assemble and provide NHC binding sites, while AuNPs served as the inorganic component due to NHCs’ strong affinity for gold surfaces. The resulting peptoid-NHC@AuNPs form well-defined vesicles that are characterized by UV–vis spectroscopy, X-ray photoelectron spectroscopy, and electron microscopy. Importantly, the vesicle size and morphology can be tuned via the peptoid sequence or environmental conditions. Further experiments highlight the crucial role of the NHC sites in the formation and stabilization of these nanohybrids. This modular strategy offers a versatile route to fabricating functional NHC-based nanohybrids for potential applications in sensing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Influence of Surface Defects on WO 3 Photoelectrodes for Catalyzing Chloride Oxidation in Water

Tungsten oxide (WO 3 ) is an n-type semiconductor due to oxygen vacancies (□ O •• in Kroger-Vink notation) or surface protonation as H x WO 3 . It is one of the few acid-stable oxides under large positive bias, which makes WO 3 ideal for interrogating the mechanism of the chloride oxidation reaction (COR). The large, positive valence band edge of ∼3 eV provides the overpotential necessary to carry out the COR, but the reaction competes with the oxygen-evolution reaction in water. The □ O •• defect density can be controlled by the atmosphere under which the material is annealed, so WO 3 films were prepared by a spin-coating method from an ammonium metatungstate precursor annealed at 500 °C under air, flowing O 2 , and flowing argon. Annealing the films in a flowing O 2 atmosphere hinders the formation of □ O ••, and annealing in Ar leads to greater surface W 6+ , likely due to expelling intercalated H + . The saturated photocurrent density (j ph ) is highest in films with the greatest concentration of W 5+ and greatest concentration of oxide defects: (0.66 mA/cm 2 annealed in air, 0.58 mA/cm 2 annealed in Ar, and 0.49 mA/cm 2 annealed in O 2 , reported at 1.5 V vs Ag/AgCl, pH 3 (before the onset of a dark reaction). The defect concentrations are determined by X-ray photoelectron spectroscopy. In all cases the Faradaic efficiency for the COR is near unity. Finally, we demonstrate that W 5d states can be probed by ligand K-edge X-ray absorption near-edge spectroscopy via pre-edge (Cl 1s → W 5d) transitions, lower in energy than the ligand-centered (Cl 1s → 4p) transition. We use this analysis to show the presence of W─Cl covalent bonds on the WO 3 films post-COR, corroborated by DFT calculations. Furthermore, this result stands in contrast to the commonly assumed mechanistic proposal invoking outer-sphere electron transfer to a physisorbed chloride ion.

Cl K-edge↗
DOE OSTI2025

Carbene Functionalization of Monolayer Tungsten Disulfide for Enhanced Quantum Emission

Semiconducting two-dimensional (2D) transition metal dichalcogenides (TMDs) are promising materials for an array of applications, ranging from conventional field-effect transistors, photodetectors, and light-emitting diodes to their more recent use in quantum photonic technologies. Chemical functionalization of 2D TMDs with organic ligands and adlayers provides an additional means for customizing their electronic and optical properties. While many pathways have been reported for the chemical functionalization of 2D TMDs, their frequent reliance on solution-based methods results in limited control over adlayer thickness and coverage, thus hindering utility in high-performance applications. Here, in this study, we describe the vapor-phase functionalization of a 2D TMD with carbene ligands, specifically tungsten disulfide (WS 2 ) with N-heterocyclic carbenes (NHCs), resulting in molecularly smooth, thin, and uniform adlayers. Reacting NHCs with monolayer WS 2 reduces the broad photoluminescence background observed at cryogenic temperatures by 58%, which facilitates the detection of single-photon emitters from strained monolayer WS 2 , as indicated by second order correlation values ( g (2) ) as low as 0.17 ± 0.07. Chemical characterization coupled with density functional theory calculations suggests that the NHC adlayer has a dual defect-passivation and doping effect on monolayer WS 2 that results in enhanced single-photon emission. Overall, this study establishes vapor-phase carbene functionalization as a homogeneous surface modification scheme for tailoring the quantum emission properties of semiconducting 2D TMDs.

N-heterocyclic carbenes↗
DOE OSTI2025

Plutonium Oxidation State Distribution in the Presence of WIPP-Relevant Organics and Iron Corrosion Products

The oxidation state and solubility of plutonium (Pu) in high ionic strength synthetic WIPP (Waste Isolation Pilot Plant) brines as a function of pC H+ in the presence and absence of WIPP-relevant organic ligands (EDTA [Ethylenediaminetetraacetic acid], oxalate, citrate, acetate) and iron corrosion products (magnetite and metallic iron) at 𝑇 = 23 ± 2 ∘C was thoroughly studied by long-term batch solubility experiments (between approximately 800-1,100 days) from an undersaturation approach. The oxidation state of Pu in the WIPP environment has been a topic of interest since the initial Compliance Certification Application (CCA). This study aims to investigate the solubility of Pu under the expected WIPP conditions and to determine the oxidation state of the solid phase that will control the solubility. One of the most important results of this study is that the Pu oxidation state was analyzed both from the surface area of the corrosion products and in the precipitated solid. The analysis of the Pu oxidation state on the surface of the iron mineral from the ongoing undersaturated experiments is more relevant to the performance assessment of nuclear waste disposal than short term batch (plutonium-iron phase) experiments. The X-ray Absorption Near-Edge Spectroscopy (XANES) analysis showed that Pu oxidation state is different on the metal surface and in the precipitated solid. Pu(III) is the dominant oxidation state in the metallic iron (Fe 0 ) system in the presence and absence of organics. Pu(IV) is the dominant oxidation state in the magnetite system in the presence and absence of organics. Also, organics stabilize Pu(IV) in the magnetite system. Analysis of Pu in the precipitated solid by Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that Pu formed an inner-sphere complex with iron with minor amounts of PuO 2 present. X-ray diffraction (XRD) results indicate that metallic iron and magnetite did not oxidize in three years in the alkaline and high ionic strength system. Under these conditions (8 < pC H+ < 10 at T = (22 ± 2) °C under nitrogen atmosphere, the solubility of Pu changes by up to three orders of magnitude (10 -5 and 10 -8 M). The spread in solubility is highest at pC H+ = 9. Pu(III) and Pu(IV) showed different solubility behavior in the synthetic WIPP brine. A summary of the data collected in this report will be submitted to Sandia National Laboratories as part of a parameter update report which will outline the changes to the OXSTAT parameter for the 2026 Compliance Recertification Application (CRA-2026). The experiments performed were done according to the U.S. Department of Energy (DOE) approved Test Plan entitled “Effects of Radiolysis, Organic Complexation, and Redox Conditions on the Speciation and Oxidation State Distribution of Pu(III/IV)” (LCO-ACP-25). All data reported were obtained under the Los Alamos National Laboratory-Carlsbad Office (LANL-CO) Quality Assurance Program, which is compliant with the DOE Carlsbad Field Office, Quality Assurance Program Document (CBFO/QAPD).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Ligand-induced self-assembly of twisted two-dimensional halide perovskites

Two-dimensional (2D) halide perovskites (HPs) exhibit intriguing optoelectronic functionalities. Conventionally, 2D HPs have been synthesized with linear and planar molecular spacers, resulting in nominal modifications of their optoelectronic properties. In contrast, lower-dimensional HPs (0D and 1D) have proved accommodating to the incorporation of bulky molecular spacers. Fundamental insights into the incorporation of bulky molecular spacers in 2D HP structures remains elusive. Here, in this study, by implementing a high-throughput autonomous exploration workflow, the crystallization behaviours of 2D HPs based on a bulky 3,3-diphenylpropylammonium (DPA) spacer are comprehensively explored. Counterintuitive to conventional HP chemistry, synthesis of 2D DPA 2 PbI 4 HPs is indeed feasible when the steric hindrance is mediated by minute incorporation of 3D HP precursors. Furthermore, a moiré superlattice is observed from the DPA 2 PbI 4 flakes, indicating the spontaneous formation of twisted stacks of 2D HPs.We hypothesize that the unconventional van der Waals surface of DPA 2 PbI 4 facilitates the self-assembly of the twisted stacks of 2D HPs. This work exemplifies how high-throughput experimentation can discover unconventional material systems in which the synthetic principle lies beyond conventional chemical intuition. Furthermore, these findings provide hints for how to chemically manipulate the twist stacking in 2D HPs, thus rendering a straightforward way for bespoke realization of functionalities in exotic materials systems via a bottom-up approach.

materials chemistry↗
NASA NTRS2023

Colorimetric and Label-Free Optical Detection of Pb 2+ Ions via Colloidal Gold Nanoparticles

The detection of Lead (Pb) heavy metal in water is crucial in many chemical processes as it is associated with serious health hazard. Here, we report the selective and precise colorimetric detection of Pb 2+ ions in water exploiting the mechanisms of aggregation and self-assembly of Glutathione (GSH) functionalized gold nanoparticles (GNPs). The carboxyl functional groups are available to create coordination complexes with Pb 2+ inducing aggregation amongst the GSH-GNPs in the presence of Pb 2+ due to the chelation of the GSH ligands. The resulting aggregation of amongst the GSHGNPs in the presence of Pb2+ increases the aggregate size depending on available Pb 2+ ions affecting the plasmonic coupling. This causes in a substantial shift in the plasmon wavelength to a longer wavelength side with increasing Pb 2+ concentration, resulting in a red-to-blue colorimetric or visual change, enabling instant determination of lead content in water.

calorimetric detection↗
DOE OSTI2024

p K a of alcohols dictates their reactivity with reduced uranium-substituted thiomolybdate clusters

The uranium-substituted thiomolybdate cluster, (Cp* 3 Mo 3 S 4 )UCp*, has been demonstrated as a model for water reduction by single uranium atoms supported on a molybdenum sulfide surface (U@MoS 2 ). In this study, the scope of O–H bond activation is expanded through the investigation of the reactivity of various alcohols with differing pKa values for the –OH proton. The reaction of (Cp* 3 Mo 3 S 4 )UCp* with stoichiometric amounts of methanol, phenol, 2,6-dichlorophenol, and nonafluoro-tert-butyl alcohol affords the corresponding mono-alkoxide species, (Cp* 3 Mo 3 S 4 )Cp*U(OR), via a uranium-metalloligand cooperative activation of the O–H bond. This observed reactivity is analogous to the O–H bond activation reported by (Cp* 3 Mo 3 S 4 )UCp* in the presence of water. However, addition of tert-butanol induces protonolysis of the Cp* ligand on uranium, resulting in the formation of a uranium tris-tert-butoxide cluster, (Cp* 3 Mo 3 S 4 )U(O t Bu) 3 . Independent synthesis of (Cp* 3 Mo 3 S 4 )Cp*U(O t Bu) was possible via an alternative pathway, eliminating sterics as a justification for the observed discrepancy in reactivity. Furthermore, these results offer insight into the role the –OH proton pKa plays in dictating the mechanism of O–H bond activation of alcohols by the uranium-substituted thiomolybdate cluster.

Patra, Kamaless↗
DOE OSTI2025

Effect of growth dynamics on the structural, photophysical and pseudocapacitance properties of famatinite copper antimony sulphide colloidal nanostructures (including nanosheets)

Facile phase selective synthesis of copper antimony sulphide (CAS) nanostructures is important because of their tunable photoconductive and electrochemical properties. In this study, off-stoichiometric famatinite phase CAS (fCAS) quasi-spherical and quasi-hexagonal colloidal nanostructures (including nanosheets) of sizes, 2.4–18.0 nm were grown under variable conditions of temperature (60–200 °C), time and oleylamine capping ligand concentration using copper(II) acetylacetonate and antimony(III) diethyldithiocarbamate precursors. Data from powder X-ray diffraction, Raman spectroscopy and high-resolution scanning/transmission electron microscopy confirm the tetragonal structure of the famatinite phase. X-ray photoelectron spectroscopy, transmission electron microscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy data suggest a correlation of particle size, morphology and composition of the off-stoichiometric fCAS nanostructures with growth temperature and time, and oleylamine concentration. The off-stoichiometric Cu 3-a Sb 1+b S 4±c (a, b, c – mole fractions) nanostructures being severely copper-deficient and antimony-rich, exhibit shallow-lying acceptor copper vacancy states, deep-lying donor states of antimony interstitials, sulphur vacancies and antimony-copper antisites and shallow-lying acceptor surface trapping states. Further, these electronic states are likely implicated in tunable UV-visible absorption and bandgaps between 2.3 and 2.8 eV, and broad visible-NIR photoluminescence with fast recombination of radiative lifetimes between 0.2 and 6.2 ns, confirmed from absorption, steady-state and time-resolved photoluminescence spectroscopies. Additionally, cyclic voltammetry and electrochemical impedance spectroscopy confirm that electrodes of the fCAS nanostructures display slightly variable pseudocapacitance of charge-storage primarily via possible sodium ion intercalation with a high specific capacitance of ~84 F g -1 obtained at a scan rate of 5 mV s -1 . Overall, these results show the influence of composition, in particular point defects, phase quality and morphology on the optical and pseudocapacitance properties of fCAS nanostructures, suitable as solar absorbers or electrodes for energy storage devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Selective Reduction of Carbon Dioxide in Water Using [M(bpy2+)(CO)3(I)]2+ (M = Mn, Re) Electrocatalysts with Pendent Cations

Manganese(I) carbonyl complexes are promising electrocatalysts for CO2 reduction, yet their application in homogeneous aqueous media remains limited by poor solubility and selectivity. Here, we report water-soluble Mn(I) and Re(I) complexes fac-[M(bpy2+)(CO)3X]2+ (X = I or Cl), featuring bipyridine ligands functionalized with -Ph-CH2-(NMe3)+ cationic ammonium groups that integrate water solubility with secondary-sphere stabilization. In bicarbonate buffer at pH 6.8, the Mn catalyst is completely selective for CO production at a low overpotential (η = 0.3 V), operating by a protonation-first mechanism with observed rates of ~10 s−1. Pulse radiolysis reveals that the one-electron reduced Mn species undergoes dimerization in the absence of CO2 but uniquely reacts competitively with CO2 through an initial pre-equilibrium followed by fast formation of a dinuclear CO2-bridged species (ΔGo = −12.4 kcal mol−1). At a higher 0.6 V over-potential, a faster reduction-first pathway (~100 s−1) is available upon reduction of the metallo-carboxylic acid intermediate, Mn-CO2H2+; however, this regime is functionally limited by the formation of a resistive, noncatalytic film on the electrode surface. Comparison to the analo-gous water-soluble Re catalyst (kobs = 440 s−1, η = 0.6 V) highlights the distinct mechanistic ad-vantages of earth-abundant Mn in low-potential catalysis. These results demonstrate how cati-onic second-sphere design enables selective, homogeneous CO2 reduction in water while reveal-ing competing radical and electrode-mediated processes that govern catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Femtosecond Core-Level Spectroscopy Reveals Involvement of Triplet States in the Gas-Phase Photodissociation of Fe(CO) 5

Excitation of iron pentacarbonyl [Fe(CO) 5 ], a prototypical photocatalyst, at 266 nm causes the sequential loss of two CO ligands in the gas phase, creating catalytically active, unsaturated iron carbonyls. Despite numerous studies, major aspects of its ultrafast photochemistry remain unresolved because the early excited-state dynamics have so far eluded spectroscopic observation. This has led to the long-held assumption that ultrafast dissociation of gas-phase Fe(CO) 5 proceeds exclusively on the singlet manifold. Herein, we present a combined experimental–theoretical study employing ultrafast extreme ultraviolet transient absorption spectroscopy near the Fe M 2,3 -edge, which features spectral evolution on 100 fs and 3 ps time scales, alongside high-level electronic structure theory, which enables characterization of the molecular geometries and electronic states involved in the ultrafast photodissociation of Fe(CO) 5 . We assign the 100 fs evolution to spectroscopic signatures associated with intertwined structural and electronic dynamics on the singlet metal-centered states during the first CO loss and the 3 ps evolution to the competing dissociation of Fe(CO) 4 along the lowest singlet and triplet surfaces to form Fe(CO) 3 . Calculations of transient spectra in both singlet and triplet states as well as spin–orbit coupling constants along key structural pathways provide evidence for intersystem crossing to the triplet ground state of Fe(CO) 4 . Finally, our work presents the first spectroscopic detection of transient excited states during ultrafast photodissociation of gas-phase Fe(CO) 5 and challenges the long-standing assumption that triplet states do not play a role in the ultrafast dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗