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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Synthesis and Characterization of Layered Actinide (U, Np, Pu) Oxide and Hydroxide Phases

Systematic structural comparisons across the early actinides remain limited by the scarcity of well-defined transuranic layered oxide and oxyhydroxide phases. Here, we report the synthesis and single-crystal characterization of new layered actinide compounds spanning U, Np, and Pu obtained under mild hydrothermal conditions in concentrated alkali hydroxide media. These include hydrated oxides α-Cs 2 U 2 O 7 •0.5H 2 O and Rb 2 An 2 O 7 •0.5H 2 O (An = Np, Pu), oxy-hydroxides Rb 6 [(AnO 2 ) 6 O 8 (OH) 2 ]•xH 2 O x = 0, 0.5 (An = U, Np) and Rb 4 [(UO 2 ) 5 O 6 (OH) 2 ]•2H 2 O, as well as nitrate-intercalated compounds Cs 6 [(AnO 2 ) 3 O 4 (OH) 2 ](NO 3 ) 2 (An = Np, Pu). Single-crystal X-ray diffraction studies reveal extended two-dimensional architectures constructed from edge- and vertex-sharing actinyl polyhedra, with systematic evolution in equatorial coordination, hydration, and anionic sheet topology across the U–Np–Pu series. Incorporation of nitrate anions within the interlayer region of Cs 6 [(AnO 2 ) 3 O 4 (OH) 2 ](NO 3 ) 2 establishes a previously unobserved structural motif in layered transuranic oxyhydroxides, demonstrating an additional pathway for anion-mediated framework stabilization. Correlation of crystallographic metrics with single-crystal Raman spectroscopy provides new vibrational benchmarks linking differences in An═O yl bond lengths to the equatorial coordination and the interstitial cations. These findings expand the structural hierarchy of layered actinide materials and address clarifying periodic trends governing topology, bonding, and vibrational signatures in high-valent 5ƒ oxide systems.

actinides↗
DOE OSTI2020

Dynamics of Cation-Induced Conformational Changes in Nanometer-Sized Uranyl Peroxide Clusters

Conformational changes of the pyrophosphate (Pp)-functionalized uranyl peroxide nanocluster [(UO 2 ) 24 (O 2 ) 24 (P 2 O 7 ) 12 ] 48– ({U 24 Pp 12 }), dissolved as a Li/Na salt, can be induced by the titration of alkali cations into solution. The most symmetric conformer of the molecule has idealized octahedral ( O h ) molecular symmetry. One-dimensional 31 P NMR experiments provide direct evidence that both K + and Rb + ions trigger an O h -to- D 4 h conformational change within {U 24 Pp 12 }. Variable-temperature 31 P NMR experiments conducted on partially titrated {U 24 Pp 12 } systems show an effect on the rates; increased activation enthalpy and entropy for the D 4 h -to- O h transition is observed in the presence of Rb + compared to K + . Two-dimensional, exchange spectroscopy 31 P NMR revealed that magnetization transfer links chemically unique Pp bridges that are present in the D 4 h conformation and that this magnetization transfer occurs via a conformational rearrangement mechanism as the bridges interconvert between two symmetries. The interconversion is triggered by the departure and reentry of K (or Rb) cations out of and into the cavity of the cluster. This rearrangement allows Pp bridges to interconvert without the need to break bonds. Cs ions exhibit unique interactions with {U 24 Pp 12 } clusters and cause only minor changes in the solution 31 P NMR signatures, suggesting that O h symmetry is conserved. Single-crystal X-ray diffraction measurements reveal that the mixed Li/Na/Cs salt adopts D 2 h molecular symmetry, implying that while solvated, this cluster is in equilibrium with a more symmetric form. Thus, these results highlight the unusually flexible nature of the actinide-based {U 24 Pp 12 } and its sensitivity to countercations in solution.

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

Cholesky Decomposition-Based Implementation of Relativistic Two-Component Coupled-Cluster Methods for Medium-Sized Molecules

A Cholesky decomposition (CD)-based implementation of relativistic two-component coupled-cluster (CC) and equation-of-motion CC (EOM-CC) methods using an exact two-component Hamiltonian augmented with atomic-mean-field integrals (the X2CAMF scheme) is reported. Furthermore, the present CD-based implementation of X2CAMF-CC and EOM-CC methods employs atomic-orbital-based algorithms to avoid the construction of two-electron integrals and intermediates involving three and four virtual indices. The CD-based implementation extends the applicability of X2CAMF-CC and EOMCC methods to medium-sized molecules with the correlation of around 1000 spinors. Benchmark calculations for uranium-containing small molecules have been performed to assess the dependence of CC results with respect to the Cholesky threshold. A Cholesky threshold of 10 –4 is shown to maintain chemical accuracy. Example calculations to illustrate the capability of the CD-based relativistic CC methods are reported for the bond dissociation energy of the uranium hexafluoride molecule, UF 6 , with up to quadruple-zeta basis sets and the lowest excitation energy in solvated uranyl ion [UO 2 2+ (H 2 O) 12 ].

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

Data-Driven Kinetic Reaction Networks for Separation Chemistry

Understanding complex, multistep chemical reactions at the molecular level is a major challenge whose solution would greatly benefit the design and optimization of numerous chemical processes. The separation of rare-earth (4f) and actinide (5f) elements is an example where improving our chemical understanding is important for designing and optimizing new chemistries, even with a limited number of observations. Here, in this work, we leverage data-driven artificial intelligence and machine-learning approaches to develop kinetic reaction networks that describe the liquid–liquid extraction mechanism of uranium using N,N-di-2-ethylhexyl-isobutyramide (DEHiBA). Specifically, we compare and contrast the properties of two classes of models: (1) purely data-driven models that are regularized using chemistry-agnostic, L1 regression and (2) chemistry-informed models that are regularized using relative reaction energies provided by quantum mechanical calculations. We observe that purely data-driven models are unbiased, simple, and accurate in their predictions of experimental measurements when provided with sufficient data but are difficult to fully constrain and interpret. In contrast, chemistry-informed models exhibit significantly improved chemical interpretability and consistency, providing a detailed description of the separation process while achieving high accuracy through ensemble averaging. Overall, the dominant species predicted to be extracted into the organic phase is UO 2 (NO 3 ) 2 (DEHiBA) 2 , agreeing with experimental slope analysis, thermodynamic modeling, EXAFS, and crystal structures. This work demonstrates that leveraging the fundamental structure of the problem can lead to efficient learning schemes that provide both accurate predictions and chemical insights at a low computational cost.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Interplay between London Dispersion, Hubbard U , and Metastable States for Uranium Compounds

High-throughput computational studies of lanthanide and actinide chemistry with density-functional theory are complicated by the need for Hubbard U corrections, which ensure localization of the f-electrons, but can lead to metastable states. This work presents a systematic investigation of the effects of both Hubbard U value and metastable states on the predicted structural and thermodynamic properties of four uranium compounds central to the field of nuclear fuels: UC, UN, UO 2 , and UCl 3 . We also assess the impact of the exchange-hole dipole moment (XDM) dispersion correction on the computed properties. Overall, the choice of Hubbard U value and inclusion of a dispersion correction cause larger variations in the computed geometric properties than result from metastable states. Further, the weak dependence of structure optimization on metastable states should simplify future high-throughput calculations on actinides. Conversely, addition of the dispersion correction is found to offset the repulsion introduced by the Hubbard U term and provides greatly improved agreement with experiment for both cell volumes and heats of formation. The XDM dispersion correction is largely invariant to the chosen U value, making it a robust dispersion correction for actinide systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Theoretical and Experimental Study of the Spectroscopy and Thermochemistry of UC +/0/–

A combination of high-level ab initio calculations and anion photoelectron detachment (PD) measurements is reported for the UC, UC – , and UC + molecules. To better compare the theoretical values with the experimental photoelectron spectrum (PES), a value of 1.493 eV for the adiabatic electron affinity (AEA) of UC was calculated at the Feller–Peterson–Dixon (FPD) level. The lowest vertical detachment energy (VDE) is predicted to be 1.500 eV compared to the experimental value of 1.487 ± 0.035 eV. A shoulder to lower energy in the experimental PD spectrum with the 355 nm laser can be assigned to a combination of low-lying excited states of UC – and excited vibrational states. The VDEs calculated for the low-lying excited electronic states of UC at the SO-CASPT2 level are consistent with the observed additional electron binding energies at 1.990, 2.112, 2.316, and 3.760 eV. Potential energy curves for the Ω states and the associated spectroscopic properties are also reported. Compared to UN and UN + , the bond dissociation energy (BDE) of UC (411.3 kJ/mol) is predicted to be considerably lower. The natural bond orbitals (NBO) calculations show that the UC 0/+/– molecules have a bond order of 2.5 with their ground-state configuration arising from changes in the oxidation state of the U atom in terms of the 7s orbital occupation: UC (5f 2 7s 1 ), UC – (5f 2 7s 2 ), and UC + (5f 2 7s 0 ). Furthermore, the behavior of the UN and UC sequence of molecules and anions differs from the corresponding sequences for UO and UF.

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

ThO 2 and Th 1– x U x O 2 Nanoscale Materials and Thin Films for Nuclear Science Applications

This study investigates the dynamics and mechanisms of solution combustion synthesis (SCS) for the preparation of nanoscale ThO 2 and Th 1–x U x O 2 materials, utilizing metal nitrates (Th(NO 3 ) 4 and UO 2 (NO 3 ) 2 ) and acetylacetone (C 5 H 8 O 2 ) as reactants dissolved in a 2-methoxyethanol (C 3 H 8 O 2 ) solvent. By combining thermodynamic calculations, dynamic time–temperature profile measurements with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), this research reveals how variations in acetylacetone concentration and uranium content influence the structural parameters of the synthesized oxides. The time–temperature measurements show that the heating rate and maximum combustion temperatures are sensitive to acetylacetone concentration. DSC-TGA results indicate shifts in exothermic peak temperatures as the uranium content changes. The complexation between thorium and acetylacetone emerges as a critical factor, impacting combustion parameters and the structural characteristics of the final products. The uniform distribution of Th and U in the Th 1–x U x O 2 solid solution and the formation of nanoscale particles with strained crystallites are considered essential for the low-temperature densification of these materials for nuclear fuel pellet applications. Additionally, high-quality ThO 2 and Th 1–x U x O 2 thin (100–150 nm) films are successfully synthesized via electrospray deposition of combustible solutions followed by a brief period of heat treatment. Furthermore, these films exhibit excellent structural and morphological uniformity, making them ideal candidates for nuclear measurements, irradiation damage studies, and investigations into the physical properties of both pure and mixed oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Pentavalent Uranium Enriched Mineral Surface under Electrochemically Controlled Reducing Environments

Redox reactions of uranium (U) in aqueous environments have important impacts on the mobility and isotopic fractionation of U in the geosphere. Pentavalent U as the cationic uranyl ion, UO 2 +, is rarely observed in naturally occurring samples because of its limited lifetime, but it may be an important intermediate state controlling the redox kinetics between hexavalent and tetravalent U. Increasing evidence has indicated that U(V) can be stabilized under laboratory conditions. Here, we showed that U(V) is the dominant species on the magnetite (Fe 3 O 4 ) surface under reducing conditions controlled by electrochemical methods. Cyclic voltammetry reveals coupled redox peaks corresponding to the U(VI)O 2 2+ /U(V)O 2+ one-electron redox reaction. Magnetite electrodes polarized at a series of potentials to reduce U(VI)O 2 2+ were characterized by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and Auger electron mapping. Overall, the results showed that up to twice the amount of U(V) to U(VI) was present on the magnetite surface. U(V) adopted a typical uranyl-type structure, and the U coverage on the magnetite surface increased with decreasing potentials. The formation of mixed-valence U(V)/U(VI) species on the surface of magnetite may hinder the U(V) disproportionation reaction, thereby eliminating the presence of tetravalent U. These results show that U(V) can exist over short time scales as the dominant U species on mineral surfaces under selected reducing conditions by the controlled polarization of a mineral electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A preliminary investigation into the use of molecular oxide and hydride secondary ion relationships for improvement of the 236U/238U determination on a NanoSIMS 50L

Abstract A NanoSIMS 50L is used to investigate uranium molecular ( 235 U 16 O, 236 U 16 O, 238 U 16 O, 235 U 1 H, 238 U 1 H, 236 U 16 O 1 H, and 238 U 16 O 1 H) and elemental ( 235 U, 236 U, and 238 U) secondary ion production during sputtering of synthetic UO 2 and the NIST-610 standard to determine if: (1) the 236 U 16 O/ 238 U 16 O molecular oxide ratio performs better than the 236 U/ 238 U elemental ratio, and (2) there is co-variance between the molecular hydrides and oxides. Despite an order of magnitude greater abundance of 236 U 16 O secondary ions (compared to 236 U), the 236 U 16 O/ 238 U 16 O ratios are less accurate than the 236 U/ 238 U ratios. Further work is needed before the higher count rate of the 236 U 16 O secondary ion can be used to obtain a better 236 U/ 238 U ratio. The second objective was undertaken because correction for the interference of 235 U 1 H on the 236 U secondary ion species typically utilizes the 238 U 1 H/ 238 U ratio. This becomes problematic in samples containing 239 Pu, so our aim was to understand if the hydride formation rate can be constrained independently of having to measure the 238 U 1 H. We document correlations between the hydride ( 238 U 1 H and 238 U 16 O 1 H) and oxide ( 236 U 16 O) secondary ions, suggesting that pursuing an alternative correction regime is worthwhile.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Simultaneous isotopic analysis of fission product Sr, Mo, and Ru in spent nuclear fuel particles by resonance ionization mass spectrometry

Abstract Fission product Sr, Mo, and Ru isotopes in six 10-μm particles of spent fuel from a pressurized water reactor were analyzed by resonance ionization mass spectrometry (RIMS) and evaluated for utility in nuclear material characterization. Previous measurements on these same samples showed widely varying U, Pu, and Am isotopic compositions owing to the samples’ differing irradiation environments within the reactor. This is also seen in Mo and Ru isotopes, which have the added complication of exsolution from the UO 2 fuel matrix. This variability is a hindrance to interpreting data from a collection of particles with incomplete provenance since it is not always possible to assign particles to the same batch of fuel based on isotopic analyses alone. In contrast, the measured 90 Sr/ 88 Sr ratios were indistinguishable across all samples. Strontium isotopic analysis can therefore be used to connect samples with otherwise disparate isotopic compositions, allowing them to be grouped appropriately for interpretation. Strontium isotopic analysis also provides a robust chronometer for determining the time since fuel irradiation. Because of the very high sensitivity of RIMS, only a small fraction of material in each of the 10 μm samples was consumed, leaving the vast majority still available for other analyses.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Stochastic optimization of a uranium oxide reaction mechanism using plasma flow reactor measurements

Abstract In this work, a coupled Monte Carlo Genetic Algorithm (MCGA) approach is used to optimize a gas phase uranium oxide reaction mechanism based on plasma flow reactor (PFR) measurements. The PFR produces a steady Ar plasma containing U, O, H, and N species with high temperature regions (3000–5000 K) relevant to observing UO formation via optical emission spectroscopy. A global kinetic treatment is used to model the chemical evolution in the PFR and to produce synthetic emission signals for direct comparison with experiments. The parameter space of a uranium oxide reaction mechanism is then explored via Monte Carlo sampling using objective functions to quantify the model-experiment agreement. The Monte Carlo results are subsequently refined using a genetic algorithm to obtain an experimentally corroborated set of reaction pathways and rate coefficients. Out of 12 reaction channels targeted for optimization, four channels are found to be well constrained across all optimization runs while another three channels are constrained in select cases. The optimized channels highlight the importance of the OH radical in oxidizing uranium in the PFR. This study comprises a first step toward producing a comprehensive experimentally validated reaction mechanism for gas phase uranium molecular species formation.

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

U redox state tracked in mineralized hydrothermal carbonate with implications for U-Pb geochronology

U-Pb carbonate geochronology can directly constrain the timing and rates of important geological processes. However, the mechanisms and controls on U incorporation, distribution, and retention in carbonate minerals remain unclear, limiting geological interpretations. Here X-ray absorption spectroscopy (µXAS) and in-situ U-Pb carbonate geochronology are combined to temporally track U distribution and redox state in a porphyry-epithermal system. In this setting, multiple generations of carbonate minerals record fluid conditions and processes which control the solubility and deposition of metals, including U. This novel approach provides the first evidence of both oxidized UO 2 2+ and reduced U 4+ species in temporally distinct generations of carbonate within a single sample. Preservation of two different U oxidation states during discrete precipitation events requires U retentivity within older domains, demonstrating that the U-Pb carbonate geochronometer is robust under hydrothermal conditions. Furthermore, crystal zones with abundant fluid/vapour inclusions linked to boiling processes coincide with relatively high levels of U and favourable U/Pb. Targeting carbonate domains with these textures may therefore increase success in U-Pb geochronology. U-Pb carbonate dating combined with µXAS can track the temporal evolution of processes critical for metal deposition in long-lived and multistage hydrothermal-magmatic ore deposit settings.

58 GEOSCIENCES↗
DOE OSTI2026

Multi-material direct ink writing and co-sintering of gadolinium oxide – zirconium oxide components

Methods for fabrication of multi-material or functionally graded ceramic composite architectures are of interest for numerous applications. However, conventional co-sintering of multi-material ceramic parts is a challenge because differences in the sintering behavior of the two materials leads to interfacial strain and, ultimately, component failure. Direct ink writing (DIW) is an extrusion-based additive manufacturing process that excels at multi-material printing because multiple extrusion nozzles can be installed on the same gantry system. Furthermore, the use of DIW as a method to fabricate multi-material ceramic green bodies offers an additional variable for controlling and potentially matching sintering kinetics in the slurry formulation used for two dissimilar feedstocks. In the work documented in this manuscript, we explored two strategies to successfully co-sinter multi-material ceramic oxides: slurry optimization to match sintering kinetics and material gradients to step from one material to another. This manuscript also quantifies the allowable mismatch that avoids part cracking in solid solution forming multi-material systems and discusses best strategies to reduce mismatch during co-sintering. Inks composed of gadolinium oxide (Gd 2 O 3 ) and zirconium oxide (ZrO 2 ), a surrogate for uranium oxide (UO 2 ), were thermally matched, which resulted in a sintering mismatch reduction of over 10%. It was found that ~1% mismatch is tolerable during debind cycles and that ~5% mismatch is manageable during sintering cycles after slurry formulations are optimized to match the sintering behavior. Use of continuous gradients is shown to reduce sintering mismatch, although geometric resolution may be lost due to solid solution formation.

Snarr, Patrick L. [Oak Ridge National Laboratory (↗
DOE OSTI2020

Gas-phase molybdenum-99 separation from uranium dioxide by fluoride volatility using nitrogen trifluoride

Production of the important 99m Tc medical isotope parent, molybdenum-99 ( 99 Mo), via the fissioning of high- and low-enriched uranium (HEU/LEU) targets followed by target dissolution in acid and solution-phase purification of 99 Mo is time-consuming, generates quantities of corrosive radioactive waste, and can result in the release of an array of radionuclides to the atmosphere. An alternative 99 Mo purification method has been devised that has the potential to alleviate many of these issues. Herein, we demonstrate the feasibility of a rapid Mo/Tc gas-phase separation from UO 2 . The results indicate that volatile [ 99 Mo]Mo can be captured downstream of the reacted solid mixture on a column bed (trap) of alumina; the majority of the captured [ 99 Mo]Mo can be subsequently eluted from the alumina trap with a few milliliters of water. >1.0 × 10 5 single pass decontamination of U and the collected [ 99 Mo]Mo product is demonstrated. This simple thermo-fluorination technique has the potential to provide a rapid methodology for routine 99 Mo production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Exploring the kinetics of actinyl–EDTA reduction by ferrous iron using quantum-mechanical calculations

Here, the reduction of An(VI) (An = U, Np, and Pu) to An(IV) significantly decreases its solubility and mobility. This reaction can be hindered by complexation with inorganic (e.g., carbonate) or organic ligands. Ethylenediaminetetraacetic acid (EDTA) is one such organic ligand that forms stable complexes with actinides. Therefore, it may enhance the mobility of actinides. However, the redox kinetics and mechanisms of actinyl (An(V/VI)O 2 +/2+ )–EDTA are not well characterized yet and are thus studied here using quantum-mechanical calculations. The principle is to approach the actinyl–EDTA and Fe 2+ (reductant) in small incremental steps and calculate the system energy at each distance. The overall reaction is then delineated into sub-processes (encounter frequency in bulk solution, formation of outer-sphere complex, transition from outer- to inner-sphere complex, and electron transfer), and reaction rates are determined for each sub-process. The formation of outer-sphere complexes occurs rapidly in microseconds to seconds over a wide range of actinyl concentrations (pM to μM); in contrast, the transition to the inner-sphere complex is relatively slow (milliseconds to a few seconds). Immediate electron transfer to form the pentavalent actinide is observed along the reaction path for Np(VI) and Pu(VI), but not for U(VI). Surprisingly, in acidic conditions, one of the carboxylic groups gets protonated in EDTA of [UO 2 (edta)] 2- rather than one of the amino groups. This process-based series of calculations can be applied to any redox reaction and allows the prediction of changes to the rate law and rate-limiting step in a more fundamental way for different environments

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Safely probing the chemistry of Chernobyl nuclear fuel using micro-focus X-ray analysis

Detailed chemical analysis of the solidified molten fuel still residing in the stricken Chernobyl reactor unit 4 are inferred using multi-modal micro-focus X-ray analysis of a low-radioactivity proxy. A fascinating mixture of molten UO 2 , nuclear fuel cladding, concrete, stainless steel and other nuclear reactor components, these materials behaved like lava, solidifying to form a complex, highly radioactive glass-ceramic. Using element-specific chemical probes (micro-X-ray fluorescence and X-ray absorption spectroscopy), coupled with micro-diffraction analysis, the crystalline phase assemblage of simulants of these heterogeneous materials was established, which included “chernobylite” and a range of compositions in the (U 1-x Zr x )O 2 solid solution. Novel insight to nuclear accident fuel chemistry was obtained by establishing the oxidation state and local coordination of uranium not only in these crystalline phases, but uniquely in the amorphous fraction of the material, which varied depending on the history of the nuclear lava as it flowed through the reactor. This study demonstrates that micro-focus X-ray analysis of very small fractions of material can yield rich chemical information, which can be applied to nuclear-melt down materials to aid decommissioning and nuclear fuel management at nuclear accident sites.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

A theoretical investigation of the hydrolysis of uranium hexafluoride: the initiation mechanism and vibrational spectroscopy

Depleted uranium hexafluoride (UF 6 ), a stockpiled byproduct of the nuclear fuel cycle, reacts readily with atmospheric humidity, but the mechanism is poorly understood. Here we compare several potential initiation steps at a consistent level of theory, generating underlying structures and vibrational modes using hybrid density functional theory (DFT) and computing relative energies of stationary points with double-hybrid (DH) DFT. A benchmark comparison is performed to assess the quality of DH-DFT data using reference energy differences obtained using a complete-basis-limit coupled-cluster (CC) composite method. The associated large-basis CC computations were enabled by a new general-purpose pseudopotential capability implemented as part of this work. Dispersion-corrected parameter-free DH-DFT methods, namely PBE0-DH-D3(BJ) and PBE-QIDH-D3(BJ), provided mean unsigned errors within chemical accuracy (1 kcal mol -1 ) for a set of barrier heights corresponding to the most energetically favorable initiation steps. The hydrolysis mechanism is found to proceed via intermolecular hydrogen transfer within van der Waals complexes involving UF 6 , UF 5 OH, and UOF 4 , in agreement with previous studies, followed by the formation of a previously unappreciated dihydroxide intermediate, UF 4 (OH) 2 . The dihydroxide is predicted to form under both kinetic and thermodynamic control, and, unlike the alternate pathway leading to the UO 2 F 2 monomer, its reaction energy is exothermic, in agreement with observation. Finally, harmonic and anharmonic vibrational simulations are performed to reinterpret literature infrared spectroscopy in light of this newly identified species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗