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At least 55 records · Page 3

Deployment of neural-network-based neutron microscopic cross sections in the Griffin reactor physics application

The capability to utilize neural networks to predict macroscopic and microscopic cross section parametric spaces has been developed for the Griffin reactor physics application. The LibTorch interface enables Griffin's MOOSE-based materials to interact with LibTorch-trained models, allowing for the evaluation of complex macroscopic or microscopic cross section spaces, which are then used to evaluate the neutronic properties of the Griffin finite element model. This study benchmarks traditional ISOXML-formatted tabulation libraries against neural network-based models for 279 nuclides on 20,160 grid points for zero-dimensional and two-dimensional reactor models. Benchmark metrics include the fundamental mode eigenvalue, fission and absorption rates, and various temperature coefficients of reactivity (isothermal, fuel, and moderator). From the perspective of storage space, the complete set of LibTorch models uses 11 MB on disk, compared to the 10 GB for the ISOXML multigroup library that covers the same grid space. For the two-dimensional performance case considered in Griffin, the Torch model uses 97% less RAM than the reference ISOXML dataset while runtime increases by a factor of 3 when using the LibTorch model compared to the ISOXML dataset with multi-linear interpolation. The LibTorch model consistently yields errors within 0.01% for most analyzed quantities except for the temperature coefficients of reactivity where the maximum discrepancies are up to 0.3 $\frac{pcm}{K}$. Due to the neural network attempting to best predict quantities with no regard for a positive or negative bias for any given quantity, predictions may experience random fluctuations, resulting in both positive and negative errors. Future work will entail both depletion and coupled transient analysis to determine the predictive capabilities of Griffin with neural network-based cross sections.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Investigation of the Deactivation and Reactivation Mechanism of a Heterogeneous Palladium(II) Catalyst in the Cycloisomerization of Acetylenic Acids by In Situ XAS

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photodriven Ammonia Synthesis from Manganese Nitrides: Photophysics and Mechanistic Investigations

Ammonia synthesis from N,N,O,O-supported manganese(V) nitrides and 9,10-dihydroacridine using proton-coupled electron transfer and visible light irradiation in the absence of precious metal photocatalysts is described. While the reactivity of the nitride correlated with increased absorption of blue light, excited-state lifetimes determined by transient absorption were on the order of picoseconds. Furthermore, this eliminated excited-state manganese nitrides as responsible for bimolecular N–H bond formation. Spectroscopic measurements on the hydrogen source, dihydroacridine, demonstrated that photooxidation of 9,10-dihydroacridine was necessary for productive ammonia synthesis. Transient absorption and pulse radiolysis data for dihydroacridine provided evidence for the presence of intermediates with weak E–H bonds, including the dihydroacridinium radical cation and both isomers of the monohydroacridine radical, but notably these intermediates were unreactive toward hydrogen atom transfer and net N–H bond formation. Additional optimization of the reaction conditions using higher photon flux resulted in higher rates of the ammonia production from the manganese(V) nitrides due to increased activation of the dihydroacridine.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Femtosecond ultraviolet laser absorption spectroscopy for simultaneous measurements of temperature and OH concentration

This Letter reports a femtosecond ultraviolet laser absorption spectroscopy (fs-UV-LAS) for simultaneous in situ measurements of temperature and species. Here, this fs-UV-LAS technique was demonstrated based on X 2 Π-A 2 Σ + transitions of OH radicals near 308 nm generated in low temperature plasmas and flames. The fs-UV-LAS technique has revealed three major diagnostic benefits. First, a series of absorption features within a spectral bandwidth of ~3.2 nm near 308 nm were simultaneously measured and then enabled simultaneous multi-parameter measurements with enhanced accuracy. The results show that the temperature and OH concentration could be measured with accuracy enhanced by 29–88% and 58–91%, respectively, compared to those obtained with past two-narrow-line absorption methods. Second, an ultrafast time resolution of ~120 picoseconds was accomplished for the measurements. Third, due to the large OH X 2 Π-A 2 Σ + transitions in the UV range, a simple single-pass absorption with a 3-cm path length was allowed for measurements in plasmas with low OH number density down to ~2 × 10 13 cm –3 . Also due to the large OH UV transitions, single-shot fs absorption measurements were accomplished in flames, which was expected to offer more insights into chemically reactive flow dynamics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Effect of Redox-Inactive Metal Ion–Nickel(III) Interactions on the Redox Properties and Proton-Coupled Electron Transfer Reactivity

We report Mononuclear nickel(II) and nickel(III) complexes of a bisamidate-bisalkoxide ligand, (NMe 4 ) 2 [Ni- II (HMPAB)] (1) and (NMe 4 )[Ni III (HMPAB)] (2), respectively, have been synthesized and characterized by various spectroscopic techniques including X-ray crystallography. The reaction of redox-inactive metal ions (M n+ = Ca 2+ , Mg 2+ , Zn 2+ , Y 3+ , and Sc 3+ ) with 2 resulted in 2-M n+ adducts, which was assessed by an array of spectroscopic techniques including X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and reactivity studies. The X-ray structure of Ca 2+ coordinated to Ni(III) complexes, 2Ca 2+ T, was determined and exhibited an average Ni-Ca distance of 3.1253 angstrom, close to the metal ions' covalent radius. XAS analysis of 2-Ca 2+ and 2-Y 3+ in solution further revealed an additional coordination to Ca and Y in the 2-M n+ adducts with shortened Ni-M distances of 2.15 and 2.11 Å, respectively, implying direct bonding interactions between Ni and Lewis acids (LAs). Such a short interatomic distance between Ni(III) and M is unprecedented and was not observed before. EPR analysis of 2 and 2-M n+ species, moreover, displayed rhombic signals with g av > 2.12 for all complexes, supporting the +III oxidation state of Ni. The Ni III /Ni II redox potential of 2 and 2-M n+ species was determined, and a plot of E 1/ 2 of 2-M n+ versus pK a of [M(H 2 O) n ] m+ exhibited a linear relationship, implying that the Ni III /Ni II potential of 2 can be tuned with different redox-inactive metal ions. Reactivity studies of 2 and 2-M n+ with different 4-X-2,6-ditert-butylphenol (4-XDTBP) and other phenol derivatives were performed, and based on kinetic studies, we propose the involvement of a proton-coupled electron transfer (PCET) pathway. Analysis of the reaction products after the reaction of 2 with 4-OMe-DTBP showed the formation of a Ni(II) complex (1a) where one of the alkoxide arms of the ligand is protonated. A pK a value of 24.2 was estimated for 1a. The reaction of 2-M n+ species was examined with 4-OMe-DTBP, and it was observed that the k 2 values of 2-M n+ species increase by increasing the Lewis acidity of redox-inactive metal ions. However, the obtained k 2 values for 2-M n+ species are much lower compared to the k 2 value for 2. Such a variation of PCET reactivity between 2 and 2-M n+ species may be attributed to the interactions between Ni(III) and LAs. Our findings show the significance of the secondary coordination sphere effect on the PCET reactivity of Ni(III) complexes and furnish important insights into the reaction mechanism involving high-valent nickel species, which are frequently invoked as key intermediates in Ni-mediated enzymatic reactions, solar-fuel catalysis, and biomimetic/synthetic transformation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Observation of Plasma-Stimulated Activation of Surface Species Using Multimodal In Situ/Operando Spectroscopy Combining Polarization-Modulation Infrared Reflection-Absorption Spectroscopy, Optical Emission Spectroscopy, and Mass Spectrometry

Nonthermal plasmas (NTPs) produce reactive chemical environments, including electrons, ions, radicals, and vibrationally excited molecules, that can drive chemistry at temperatures at which such species are thermally inaccessible. There has been growing interest in the integration of conventional catalysis with reactive NTPs to promote novel chemical transformations. Unveiling the full potential of plasma-catalytic processes requires a comprehensive understanding of plasma-catalytic synergies, including characterization of plasma-catalytic surface interactions. In this work, we report on a newly designed multimodal spectroscopic instrument combining polarization-modulation infrared reflection-absorption spectroscopy (PM-IRAS), mass spectrometry, and optical emission spectroscopy (OES) for the investigation of plasma–surface interactions such as those found in plasma catalysis. In particular, this tool has been utilized to correlate plasma-phase chemistry with both surface chemistry and gas-phase products in situ (1) during the deposition of carbonaceous surface species via NTP-promoted nonoxidative coupling of methane and (2) during subsequent activation of surface deposits with an atmospheric pressure and temperature argon plasma jet on both nickel (Ni) and silicon dioxide (SiO 2 ) surfaces. For the first time, the activation of carbonaceous surface species by a NTP on Ni and SiO 2 surfaces to form hydrogen gas and C 2 hydrocarbons was directly observed, where both PM-IRAS and OES measurements suggest that they may form through different pathways. Furthermore, this unique tool for studying plasma–surface interactions could enable more rational design of plasma-stimulated catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unveiling the Degradation Nature of Pt/NbOx/C Catalysts for Oxygen Reduction Reaction via in situ X-ray Absorption Spectroscopy

Among various metal nanoparticles supported on metal oxide (MMO) catalysts, the Pt/NbOx/C system has promising oxygen reduction reaction (ORR) activity as cathode for proton exchange membrane fuel cells (PEMFCs). Herein, we study a series of Pt/NbOx/C catalysts with tunable structural and electronic properties via physical vapor deposition and unravel the nature of metal and metal oxide interaction (MMOI) by characterizing this system under reactive conditions. By conducting in situ X-ray absorption spectroscopy (XAS) experiments, we demonstrate the Pt preferably interacts with O but not Nb in the Pt/NbOx/C system and such Pt-O interaction benefits the ORR activity via electronic effect rather than strain effect. We also provide clear evidence for the formation of metallic Nb phase at the early stage of PEMFC operation and identify severe particle growth of Pt after long-term PEMFC operation. These findings deepen our understanding of the degradation mechanism of MMO catalysts during long-term PEMFC operation.

MMO catalyst↗

Engineered disorder in CO 2 photocatalysis

Light harvesting, separation of charge carriers, and surface reactions are three fundamental steps that are essential for an efficient photocatalyst. Here we show that these steps in the TiO 2 can be boosted simultaneously by disorder engineering. A solid-state reduction reaction between sodium and TiO 2 forms a core-shell c-TiO 2 @a-TiO 2-x (OH) y heterostructure, comprised of HO-Ti-[O]-Ti surface frustrated Lewis pairs (SFLPs) embedded in an amorphous shell surrounding a crystalline core, which enables a new genre of chemical reactivity. Specifically, these SFLPs heterolytically dissociate dihydrogen at room temperature to form charge-balancing protonated hydroxyl groups and hydrides at unsaturated titanium surface sites, which display high reactivity towards CO 2 reduction. This crystalline-amorphous heterostructure also boosts light absorption, charge carrier separation and transfer to SFLPs, while prolonged carrier lifetimes and photothermal heat generation further enhance reactivity. The collective results of this study motivate a general approach for catalytically generating sustainable chemicals and fuels through engineered disorder in heterogeneous CO 2 photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Isoenergetic two-photon excitation enhances solvent-to-solute excited-state proton transfer

Two-photon excitation (TPE) is an attractive means for controlling chemistry in both space and time. Since isoenergetic one- and twophoton excitations (OPE and TPE) in non-centrosymmetric molecules are allowed to reach the same excited state, it is usually assumed that they produce similar excited-state reactivity. We compare the solvent-to-solute excited-state proton transfer of the super photobase FR0-SB following isoenergetic OPE and TPE. We find up to 62% increased reactivity following TPE compared to OPE. From steady-state spectroscopy, we rule out the involvement of different excited states and find that OPE and TPE spectra are identical in non-polar solvents but not in polar ones. We propose that differences in the matrix elements that contribute to the two-photon absorption cross sections lead to the observed enhanced isoenergetic reactivity, consistent with the predictions of our high-level coupledcluster-based computational protocol. We find that polar solvent configurations favor greater dipole moment change between ground and excited states, which enters the probability for TPE as the absolute value squared. This, in turn, causes a difference in the Franck– Condon region reached via TPE compared to OPE. We conclude that a new method has been found for controlling chemical reactivity via the matrix elements that affect two-photon cross sections, which may be of great utility for spatial and temporal precision chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing time-resolved plasma-driven solution electrochemistry in a falling liquid film plasma reactor: Identification of HO$^−_2$ as a plasma-derived reducing agent

Many applications involving plasma–liquid interactions depend on the reactive processes occurring at the plasma–liquid interface. In this article, we report on a falling liquid film plasma reactor allowing for in situ optical absorption measurements of the time-dependence of the ferricyanide/ferrocyanide redox reactivity, complemented with ex situ measurement of the decomposition of formate. We found excellent agreement between the measured decomposition percentages and the diffusion-limited decomposition of formate by interfacial plasma-enabled reactions, except at high pH in thin liquid films, indicating the involvement of previously unexplored plasma-induced liquid phase chemistry enabled by long-lived reactive species. We also determined that high pH facilitates a reduction-favoring environment in ferricyanide/ferrocyanide redox solutions. In situ conversion measurements of a 1:1 ferricyanide/ferrocyanide redox mixture exceed the measured ex situ conversion and show that conversion of a 1:1 ferricyanide/ferrocyanide mixture is strongly dependent on film thickness. We identified three dominant processes: reduction faster than ms time scales for film thicknesses >100 µm, •OH-driven oxidation on time scales of <10 ms, and reduction on 15 ms time scales for film thickness <100 µm. We attribute the slow reduction and larger formate decomposition at high pH to HO$^−_2$ formed from plasma-produced H 2 O 2 enabled by the high pH at the plasma–liquid interface as confirmed experimentally and by computed reaction rates of HO$^−_2$ with ferricyanide. Overall, this work demonstrates the utility of liquid film reactors in enabling the discovery of new plasma-interfacial chemistry and the utility of atmospheric plasmas for electrodeless electrochemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experiments to Measure the Effect of Tantalum on Critical Systems

Sandia National Laboratories (SNL) and Oak Ridge National Laboratory (ORNL) collaborated to develop a capability to test the epithermal/intermediate cross sections of materials at the SNL critical experiment facility using the Seven Percent Critical Experiment (7uPCX) fuel. As a result, a new set of critical experiments has been designed to target the epithermal cross sections of tantalum (Ta) and is scheduled to be performed at SNL in 2023. These critical experiments will be evaluated for inclusion in the 2024 edition of the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Handbook. The focus of these critical experiments is to measure the effects of Ta on the critical array size. The critical array size will be determined by an approach-to-critical experiment with the number of fuel rods in the array as a free parameter. The core configurations are designed to optimize the reactivity worth of Ta and the overall percentage of Ta absorption rates in the epithermal/intermediate energy range (0.625 eV – 100 keV). The baseline core configuration includes 7uPCX fuel rods set at a triangular pitch of 1.016 cm and a central dry test region that utilizes a cadmium liner for filtering out thermal neutrons. The central test region has locations for 85 Ta rods set at a triangular pitch of 0.813 cm. The Ta reactivity worth for the case with 85 Ta rods is approximately 2.55%, with the percentage of Ta absorption rates within the intermediate energy range at nearly 90%.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Unveiling the Degradation of Pt/NbOx/C Catalysts in PEMFCs via In Situ X-ray Absorption Spectroscopy

Among the class of the catalyst that is composed of metal nanoparticles supported on metal oxides (MMO), the Pt/NbO x /C system has shown promising oxygen reduction reaction (ORR) activities as a cathode of proton exchange membrane fuel cells (PEMFCs). Herein, we have studied a series of Pt/NbO x /C catalysts prepared via physical vapor deposition and unraveled the nature of the metal and metal oxide interaction (MMOI) by characterizing this system under reactive conditions. By conducting in situ X-ray absorption spectroscopy (XAS) experiments, we demonstrate that Pt preferably interacts with O but not Nb in the Pt/NbO x /C system. As such, Pt-O interaction benefits the ORR activity via an electronic effect rather than a strain effect. We have also provided clear evidence for the formation of metallic Nb phase at the early stage of PEMFC operation, which led to severe particle growth of Pt after long-term PEMFC operation.

Electrochemistry↗

Methane Activation by a Mononuclear Copper Active Site in the Zeolite Mordenite: Effect of Metal Nuclearity on Reactivity

The direct conversion of methane to methanol would have a wide reaching environmental and industrial impact. Copper-containing zeolites can perform this reaction at low temperatures and pressures at a previously defined O 2 -activated [Cu 2 O] 2+ site. However, after autoreduction of the copper-containing zeolite mordenite and removal of the [Cu 2 O] 2+ active site, the zeolite is still methane reactive. In this study, we use diffuse reflectance UV–vis spectroscopy, magnetic circular dichroism, resonance Raman spectroscopy, electron paramagnetic resonance, and X-ray absorption spectroscopy to unambiguously define a mononuclear [CuOH] + as the CH 4 reactive active site of the autoreduced zeolite. The rigorous identification of a mononuclear active site allows a reactivity comparison to the previously defined [Cu 2 O] 2+ active site. We perform kinetic experiments to compare the reactivity of the [CuOH] + and [Cu 2 O] 2+ sites and find that the binuclear site is significantly more reactive. From the analysis of density functional theory calculations, we elucidate that this increased reactivity is a direct result of stabilization of the [Cu 2 OH] 2+ H-atom abstraction product by electron delocalization over the two Cu cations via the bridging ligand. This significant increase in reactivity from electron delocalization over a binuclear active site provides new insights for the design of highly reactive oxidative catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Absorber Optimization Study for the Terahertz Intensity Mapper (TIM)

We discuss the design and optimization of the absorber for the long-wavelength arm of the Terahertz Intensity Mapper (TIM), a balloon-borne spectrometer employing Kinetic Inductance Detectors (KIDs). Electromagnetic simulations of our design indicate in-band absorption efficiency over 80% in both linear polarization modes. By developing custom transmission line model and mode-matching calculations, we find the absorption efficiency is affected by the absorber’s reactive part and overall shape. These insights into the operation of this design provide guidance for its optimization for low-resistance absorber. materials.

Nie, Rong↗

Rotation in attosecond vibronic coherence spectroscopy for molecules

Abstract Excitation or ionization of a molecule by ultrafast laser pulses can create a superposition of electronic states, whose dynamics is influenced by the interplay of electronic coherence and nuclear motion, resulting in charge migration and possibly charge transfer. Probing the vibronic coherence is therefore vital to monitoring electronic dynamics and controlling chemical reactivity, as recently demonstrated in molecules via attosecond transient absorption spectroscopy (ATAS). However, theories supporting the interpretation of ATAS experiments neglect the effects of molecular rotation, often leading to inaccurate interpretation of experimental data. Here, we develop a comprehensive theory for ATAS of molecules encompassing the entire pump-probe process. Applying the theory to N 2 , we demonstrate that the emergence of coherent signals critically depends on the consideration of molecular rotation. This work contributes to close the gap between theory and ATAS experiments, paving the way for monitoring electronic motion and controlling chemical reactivity in diverse molecular systems.

Physics↗

Characterization of an RF-driven argon plasma at atmospheric pressure using broadband absorption and optical emission spectroscopy

Atmospheric pressure plasmas in argon are of particular interest due to the production of highly excited and reactive species enabling numerous plasma-aided applications. In this contribution, we report on absolute optical emission and absorption spectroscopy of a radio frequency (RF) driven capacitively coupled argon glow discharge operated in a parallel-plate configuration. This enabled the study of all key parameters including electron density and temperature, gas temperature, and absolute densities of atoms in highly electronically excited states. The space and time-averaged electron density and temperature were determined from the measurement of the absolute intensity of the electron-atom bremsstrahlung in the visible range. Considering the non-Maxwellian electron energy distribution function, an electron temperature (T e ) of 2.1 eV and an electron density (n e ) of 1.1 × 10 19 m –3 were obtained. The time-averaged and spatially resolved absolute densities of atoms in the metastable (1s 5 and 1s 3 ) and resonant (1s 4 and 1s 2 ) states of argon in pure Ar and Ar/He mixture were obtained by broadband absorption spectroscopy. The 1s 5 metastable atoms had the largest density near the sheath region with a maximum value of 8 × 10 17 m –3 , while all other 1s states had densities of at most 2 × 10 17 m –3 . Here, the dominant production and loss mechanisms of these atoms were discussed, in particular, the role of radiation trapping. We conclude with a comparison of the plasma properties of the argon RF glow discharges with the more common He equivalent and highlight their differences.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Photocatalytic dechlorination of unactivated chlorocarbons including PVC using organolanthanide complexes

Simple lanthanide cyclopentadienyl (Cp) complexes can photochemically cleave the sp 3 carbon–chlorine bond of unactivated chlorinated hydrocarbons including polyvinyl chloride (PVC). Further, the excited state lifetimes of these simple complexes are among the longest observed for cerium complexes (175 ns for [(Cp Me4 ) 2 Ce(μ-Cl)] 2 ) and the light absorption by the Cp ligand is efficient, so photocatalytic reactivity is enhanced for cerium and now also made possible for neighboring, normally photoinactive, lanthanide congeners.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing Parallel Inter‐ and Intra‐Ligand Charge Transfer Dynamics in [Ru(L) 2 (dppz)] 2+ Molecular Lightswitch with N K‐Edge X‐Ray Absorption Spectroscopy

In photoactive metal complexes the localization of photoexcited charges dictates the site of chemical reactivity, but few studies measure the charge redistribution in these systems with spatial precision. Herein, we track the inter- and intra-ligand charge transfer processes that underpin light-driven charge separation in the well-studied “molecular lightswitch” [Ru(bpy) 2 dppz] 2+ (aqueous [Ruthenium II (2,2′-bipyridine)2(dipyrido[3,2-a:2′,3′-c]phenazine)] 2+ [Cl − ] 2 ) by probing the electronic structure of ligand nitrogen atoms in real-time using ultrafast X-ray absorption spectroscopy and first principles calculations. We confirm the localization of excited electron density on the phenazine N atoms of dppz and we newly identify two parallel electron transfer pathways to populate this state. Sub-70 fs electron transfer to the phenazine portion of dppz is observed and attributed to intra-ligand electron transfer following Ru-to-dppz metal-to-ligand charge transfer (MLCT) excitation. This fast charge transfer was not reported in prior ultrafast studies. The slower (ca. 2 ps) charge transfer reported extensively in time-resolved optical absorption and emission studies is reassigned here to inter-ligand electron “hopping” between nearly isoenergetic ligand moieties following Ru-to-bpy MLCT excitation. In conclusion, the results demonstrate much faster charge separation than previously identified in this well-studied system, highlighting how extended azaacene ligand motifs promote the competitive charge transfer processes needed to drive light-driven electron transfer chemistry.

Donor-acceptor systems↗