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At least 469 records · Page 26

Sensitivity Testing of the NSTAR Ion Thruster

During the Extended Life Test of the DS1 flight spare ion thruster, the engine was subjected to sensitvity testing in order to characterize the macroscopic dependence of discharge chamber sensitivity to a +\-3% vatiation in main flow, cathode flow and beam current, and to +\5% variation in beam and accelerator voltage, was determined for the minimum- (THO), half- (TH8) and full power (TH15) throttle levels. For each power level investigared, 16 high/low operating conditions were chosen to vary the flows, beam current, and grid voltages in in a matrix that mapped out the entire parameter space. The matrix of data generated was used to determine the partial derivative or senitivity of the dependent parameters--discharge voltage, discharge current, discharge loss, double-to-single-ion current ratio, and neutralizer-keeper voltage--to the variation in the independent parameters--main flow, cathode flow, beam current, and beam voltage. The sensititivities of each dependent parameter with respect to each independent parameter were determined using a least-square fit routine. Variation in these sensitivities with thruster runtime was recorded over the duration of the ELT, to detemine if discharge performance changed with thruster wear. Several key findings have been ascertained from the sensitivity testing. Discharge operation is most sensitve to changes in cathode flow and to a lesser degree main flow. The data also confirms that for the NSTAR configuration plasma production is limited by primary electron input due to the fixed neutral population. Key sensitivities along with their change with thruster wear (operating time) will be presented. In addition double ion content measurements with an ExB probe will also be presented to illustrate beam ion production and content sensitivity to the discharge chamber operating parameteres.

electric propulsion↗

Determination of Pion and Kaon Structure Using the Sullivan Process at Moderate to large Fractional Momentum

Significant progress has been made in describing the structure of hadrons in terms of Quantum ChromoDynamics (QCD) degrees of freedom. The recently developed framework of Generalized Parton Distribtions (GPDs) may provide the path towards three-dimensional imaging of the hadronic structure. Integrating the GPDs over the fractional momentum (x), the form factors are obtained which are integrally related to understanding the emergent hadron mass-generating mechanism (EHM) embedded in QCD and the mass-scale that characterizes the proton [Roberts (2016)]. The Sullivan process, in which one scatters electrons off the proton?s virtual meson cloud and thus creates a meson target, is used to probe this structure. Studies of kaon electroproduction offer unique opportunities in this. The last two decades saw a dramatic improvement in the precision of charged meson form factor data, and new results have become available on the transition form factor. The KaonLT experiment (E12-09-011) carried out in Hall C at Jefferson Lab (Jlab) was designed to measure longitudinal/transverse (L/T) separated kaon cross sections required to access form factors and GPDs [Bosted et al. (2008)]. KaonLT aimed to confirm the exclusive kaon electroproduction mechanism, which is essential for determining the kaon form factor and investigating GPDs. The results obtained from this experiment have provided the highest Q2 for L-T separated kaon electroproduction cross section, and it is the first time that a separated kaon cross-section measurement has been carried out above W = 2:2GeV.

Trotta, Richard↗

Bayesian inference of nuclear symmetry energy from measured and imagined neutron skin thickness in Sn 116 , 118 , 120 , 122 , 124 , 130 , 132 , Pb 208 , and Ca 48

The neutron skin thickness Δr np in heavy nuclei has been known as one of the most sensitive terrestrial probes of the nuclear symmetry energy E sym (ρ) around $\frac{2}{3}$ of the saturation density ρ 0 of nuclear matter. Existing neutron skin data mostly from hadronic observables suffer from large uncertainties and their extraction from experiments are often strongly model dependent. While waiting eagerly for the promised model-independent and high-precision neutron skin data for 208 Pb and 48 Ca from the parity-violating electron scattering experiments (PREX-II and CREX at JLab as well as MREX at MESA), within the Bayesian statistical framework using the Skyrme-Hartree-Fock model we infer the posterior probability distribution functions (PDFs) of the slope parameter L of the nuclear symmetry energy at ρ 0 from imagined Δr np ( 208 Pb)=0.15, 0.20, and 0.30 fm with a 1σ error bar of 0.02, 0.04, and 0.06 fm, respectively, as well as Δr np ( 48 Ca)=0.12, 0.15, and 0.25 fm, with different 1σ error bar of 0.01 and 0.02 fm, respectively. The results are compared with the PDFs of L inferred using the same approach from the available Δr np data for 116, 118, 120, 122, 124, 130, 132 Sn from hadronic probes. They are also compared with results from a recent Bayesian analysis of the radius and tidal deformability data of canonical neutron stars from GW170817 and NICER. The neutron skin data for Sn isotopes gives L = 45.5 $^{+ 26.5}_{-21.6}$ MeV surrounding its mean value or L = 53 . 4 $^{+ 18.6}_{ -29.5}$ MeV surrounding its maximum a posteriori value, respectively, with the latter smaller than but consistent with the L = 66 $^{+ 12}_{-20}$ MeV from the neutron star data within their 68% confidence intervals. We found that Δr np = 0.17 –0.18 fm in 208 Pb with an error bar of about 0.02 fm leads to a PDF of L compatible with that from analyzing the Sn data. To provide additionally useful information on L extracted from the Δr np of Sn isotopes, the experimental error bar of Δr np in 208 Pb should be at least smaller than 0.06 fm aimed by some current experiments. In addition, the Δr np ( 48 Ca) needs to be larger than 0.15 fm but smaller than 0.25 fm to be compatible with the Sn and/or neutron star results. To further improve our current knowledge about L and distinguish its PDFs in the examples considered, even higher precisions leading to significantly less than ±20 MeV error bars for L at 68% confidence level are necessary.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Characteristics of Electron Precipitation During 40 Energetic Electron Injections Inferred via Subionospheric VLF Signal Propagation

Energetic electron injection events are associated with energetic electron precipitation (EEP) through possible resonant wave-particle interactions. Previous studies confirm the impacts of injection-driven precipitation on observed amplitude/phase of subionospheric VLF (very low frequency) signals transmitted from distant artificial transmitters. Currently, there are substantial uncertainties on precipitation characteristics and flux during injection events. In this work we study 40 injection events selected by Van Allen Probes particle data to investigate the changes in amplitude and phase of VLF signals at ground receivers across Canada during particle injection events. We model the ionospheric effect of the EEP flux to find its impact on VLF propagation and characterize the injection events. Typically, we find a clear phase advance of ~40° in the received VLF signal at Fort Smith (Canada, L = 8) transmitted from U.S. Navy communication transmitter NAA at Maine (USA). Comparing to other VLF transmitter-receiver paths in North America leads us to conclude that effects are only seen on paths with adequately large range >>200 km) through L > 7. Modeling the VLF phase change indicates that in the majority of events (>90%), less than 10% of the strong scattering limit inferred from particle flux measurements at the Van Allen Probes is required to obtain the observed VLF phase signature. The median precipitating flux during energetic particle injections is less than 4 × 10 6 el/cm 2 s sr (<10% of the strong scattering rate) for electrons above ~40 keV extracted from trapped particles energy spectrum. This implies that strong scattering is not typical for these 40 selected energetic electron injection events.

79 ASTRONOMY AND ASTROPHYSICS↗

A new Monte Carlo generator for BSM physics in B → K*ℓ+ℓ− decays with an application to lepton non-universality in angular distributions

Abstract Within the widely used EvtGen framework, we have added a new event generator model forB → K * ℓ + ℓ − with improved standard model (SM) decay amplitudes and possible BSM physics contributions, which are implemented in the operator product expansion in terms of Wilson coefficients. This event generator can then be used to estimate the statistical sensitivity of a simulated experiment to the most general BSM signal resulting from dimension-six operators. We describe the advantages and potential of the newly developed ‘Sibidanov Physics Generator’ in improving the experimental sensitivity of searches for lepton non-universal BSM physics and clarifying signatures. The new generator can properly simulate BSM scenarios, interference between SM and BSM amplitudes, and correlations between different BSM observables as well as acceptance bias. We show that exploiting such correlations substantially improves experimental sensitivity. As a demonstration of the utility of the MC generator, we examine the prospects for improved measurements of lepton non-universality in angular distributions forB→K * ℓ + ℓ − decays from the expected 50 ab −1 data set of the Belle II experiment, using a four-dimensional unbinned maximum likelihood fit. We describe promising experimental signatures and correlations between observables. The use of lepton-universality violating ∆-observables significantly reduces uncertainties in the SM expectations due to QCD and resonance effects and is ideally suited for Belle II with the large data sets expected in the next decade. Thanks to the clean experimental environment of ane + e − machine, Belle II should be able to probe BSM physics in the Wilson coefficientsC 7 and$$ {C}_7^{\prime } $$ C 7 ′ , which appear at lowq 2 in the di-electron channel.

Physics↗

Search for a Higgs boson produced in association with a charm quark and decaying to a W boson pair in proton-proton collisions at $ \sqrt{s}=13 $ TeV

This paper presents a search for a Higgs boson produced in association with a charm quark (cH) which allows to probe the Higgs-charm Yukawa coupling strength modifier κ$_{c}$. Higgs boson decays to a pair of W bosons are considered, where one W boson decays to an electron and a neutrino, and the other W boson decays to a muon and a neutrino. The data, corresponding to an integrated luminosity of 138 fb$^{−1}$, were collected between 2016 and 2018 with the CMS detector at the LHC at a center-of-mass energy of $ \sqrt{s}=13 $ TeV. Upper limits at the 95% confidence level (CL) are set on the ratio of the measured yield to the standard model expectation for cH production. The observed (expected) upper limit is 1065 (506), corresponding to an observed (expected) constraint of |κ$_{c}$| < 211 (95). When combined with the previous search for cH in the diphoton decay channel of the Higgs boson, the limits are interpreted as observed (expected) constraints at 95% CL on the value of κ$_{c}$, |κ$_{c}$| < 47 (51).[graphic not available: see fulltext]

Hayrapetyan, Aram [Yerevan Phys. Inst.]↗

Multi-modal dynamic radiography using short-pulse laser-generated probe beams

Radiography is an important tool for the interrogation of dynamic experiments in the fields of dynamic properties of materials, and in condensed matter, high explosive, and high-energy-density physics. Multi-modal radiography advances the hypothesis that combining the information delivered by multiple radiographic modalities can lead to more constrained (improved) “reconstruction” of the scene than can be obtained from a single probe. We identify four modalities: multi-probe, time sequence, multi-view, and multi-messenger. Multi-probe radiography is a promising candidate for a next-generation dynamic radiographic facility. High-energy X-rays are the most frequently used probe for dynamic radiography, although recent developments show the utility of proton (pRad), electron (eRad), and neutron probe beams. Because each probing species interacts with material in the radiographic scene through quantitatively different mechanisms, each returns independent information about the scene, which can add extra constraints to the reconstruction process. How to conduct detailed, quantitative “co-analysis” of multiple data streams remains an area of active research. Multi-beam, short-pulse, laser-generated probes offer sufficient dose, an appropriate spectrum, and appropriate spatio-temporal resolution to produce high-quality dynamic radiographs. This paper reports on technology development to advance the state of the art of multi-modal/multi-probe radiography and the pursuit of both deterministic and inferential (AI/ML assisted) co-analysis methodologies to produce more constrained reconstructions from multi-modal data.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Characteristics of trough region auroral patches and detached arcs observed by Isis 2

All of the data presented in this paper were obtained from the Isis 2 satellite, which was launched into a 1400-km near-circular polar orbit in April 1971. Instruments used in this study include the topside sounder for providing vertical profiles of the electron density, the Langmuir probe for measuring electron temperature and concentration, and the auroral scanning photometer for detecting optical emissions at 5577 A and 3914 A. Two distinct types of auroras (east-west-aligned oval-shaped 'patches', and isolated east-west 'detached arcs') are observed in the trough region (almost exclusively in the Northern Hemisphere) equatorward of the diffuse auroral boundary. Attention is given to comparison of patches and detached arcs, relation to magnetic indices, and relation to detached plasma and ELF hiss.

Moshupi, M. C.↗

Simultaneous rocket and MST radar observation of an internal gravity wave breaking in the mesosphere

In June, 1983, the Structure and Atmospheric Turbulence Environment (STATE) rocket and Poker Flat Mesophere-Stratosphere-Troposphere radar campaign was conducted to measure the interaction between turbulence, electron density and electron density gradient that has produced unusually strong MST radar echoes from the summer mesosphere over Poker Flat, Alaska. Analysis or radar wind measurements and a concurrent wind and temperature profile obtained from a rocket probe carrying a three-axis accelerometer are given. The two data sets provide a fairly complete (and in some cases, redundant) picture of the breaking (or more correctly, the saturation) of a large-amplitude, low-frequency, long-wavelength internal gravity wave. The data show that small-scale turbulence and small-scale wave intensity is greatest at those altitudes where the large-scale wave-induced temperature lapse rate is most negative or most nearly unstable, but the wind shear due to the large-scale wave is a minimum. A brief review of linear gravity-wave theory is presented as an aid to the identification of the gravity-wave signature in the radar and rocket data. Analysis of the time and height cross sections of wind speed and turbulence intensity observed by the Poker Flat MST radar follows. Then, the vertical profile of temperature and winds measured by a rocket probe examined. Finally, the use of the independent data sets provided by the rocket and the radar are discussed and implications for theories of wave saturation are presented.

Smith, S. A.↗

Ionospheric electron temperature at solar maximum

Langmuir-probe measurements made at solar maximum from the DE-2 satellite in 1981 and 1982 are used to examine the latitudinal variation of electron temperature at altitudes between 300 and 400 km and its response to 27-day variations of solar EUV. A comparison of these data with models based on solar-minimum measurements from the AE-C suggests that the daytime electron temperature does not change very much during the solar cycle except at low latitudes where a particularly large 27-day variation occurs. It is found that the daytime electron temperature near the F2 peak is more responsive to short-term variations in F10.7 than to any longer-term changes that may occur between solar minimum and maximum.

Brace, L. H.↗

Vibrational and Rovibrational Spectroscopy Applied to Astrochemistry

The detection of molecules in astrophysical environments almost always requires remote sensing. While radioastronomical observation and associated rotational spectroscopy are powerful astronomical tools, infrared spectral analysis provides a unique means of examining the observable universe, especially for molecules where permanent dipole moments are small or even non-existent. The molecular vibrations of small molecules are now able to be modeled via quantum chemistry and electronic structure theory conjoined to vibrational analysis to within spectroscopic accuracy in many cases. This chapter will showcase this success and build upon it to show how such advances are now being leveraged to describe molecular vibrations for molecules containing dozens of atoms, electronically excited states, "hot bands," exoplanetary atmospheric opacity data, and even emission of polycyclic aromatic hydrocarbons. All of these are required to prune the interstellar spectral garden of its "weeds" in search of "flowers" that will provide the necessary fingerprints for astronomers to be able to probe the heavens for its past, present, and future secrets.

Ryan C. Fortenberry↗

PIONEER: Studies of Rare Pion Decays

A next-generation rare pion decay experiment, PIONEER, is strongly motivated by several inconsistencies between Standard Model (SM) predictions and data pointing towards the potential violation of lepton flavor universality. It will probe non-SM explanations of these anomalies through sensitivity to quantum effects of new particles even if their masses are at very high scales. Measurement of the charged-pion branching ratio to electrons vs. muons $R_{e/\mu}$ is extremely sensitive to new physics effects. At present, the SM prediction for $R_{e/\mu}$ is known to 1 part in $10^4$, which is 15 times more precise than the current experimental result. An experiment reaching the theoretical accuracy will test lepton flavor universality at an unprecedented level, probing mass scales up to the PeV range. Measurement of pion beta decay, $\pi^+\to \pi^0 e^+ \nu (\gamma)$, with 3 to 10-fold improvement in sensitivity, will determine $V_{ud}$ in a theoretically pristine manner and test CKM unitarity, which is very important in light of the recently emerged tensions. In addition, various exotic rare decays involving sterile neutrinos and axions will be searched for with unprecedented sensitivity. The experiment design benefits from experience with the recent PIENU and PEN experiments at TRIUMF and the Paul Scherrer Institut (PSI). Excellent energy and time resolutions, greatly increased calorimeter depth, high-speed detector and electronics response, large solid angle coverage, and complete event reconstruction are all critical aspects of the approach. The PIONEER experiment design includes a 3$\pi$ sr 25 radiation length calorimeter, a segmented low gain avalanche detector stopping target, a positron tracker, and other detectors. Using intense pion beams, and state-of-the-art instrumentation and computational resources, the experiments can be performed at the PSI ring cyclotron.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A Gapped Phase in Semimetallic T d -WTe 2 Induced by Lithium Intercalation

The Weyl semimetal WTe 2 has shown several correlated electronic behaviors, such as the quantum spin Hall effect, superconductivity, ferroelectricity, and a possible exciton insulator state, all of which can be tuned by various physical and chemical approaches. A new electronic phase in WTe 2 induced by lithium intercalation is discovered. The new phase exhibits an increasing resistivity with decreasing temperature and its carrier density is almost two orders of magnitude lower than the carrier density of the semimetallic T d phase, probed by in situ Hall measurements as a function of lithium intercalation. The theoretical calculations predict the new lithiated phase to be a potential charge density wave (CDW) phase with a bandgap of ≈0.14 eV, in good agreement with the in situ transport data. The new phase is structurally distinct from the initial T d phase, characterized by polarization-angle-dependent Raman spectroscopy, and large lattice distortions close to 6% are predicted in the new phase. This finding of a new gapped phase in a 2D semimetal demonstrates electrochemical intercalation as a powerful tuning knob for modulating electron density and phase stability in 2D materials.

36 MATERIALS SCIENCE↗

Data-guided Multi-Map variables for ensemble refinement of molecular movies

Driving molecular dynamics simulations with data-guided collective variables offer a promising strategy to recover thermodynamic information from structure-centric experiments. In this study, the three-dimensional electron density of a protein, as it would be determined by cryo-EM or x-ray crystallography, is used to achieve simultaneously free-energy costs of conformational transitions and refined atomic structures. Unlike previous density-driven molecular dynamics methodologies that determine only the best map-model fits, our work employs the recently developed Multi-Map methodology to monitor concerted movements within equilibrium, non-equilibrium, and enhanced sampling simulations. Construction of all-atom ensembles along the chosen values of the Multi-Map variable enables simultaneous estimation of average properties, as well as real-space refinement of the structures contributing to such averages. Using three proteins of increasing size, we demonstrate that biased simulation along the reaction coordinates derived from electron densities can capture conformational transitions between known intermediates. The simulated pathways appear reversible with minimal hysteresis and require only low-resolution density information to guide the transition. The induced transitions also produce estimates for free energy differences that can be directly compared to experimental observables and population distributions. The refined model quality is superior compared to those found in the Protein Data Bank. We find that the best quantitative agreement with experimental free-energy differences is obtained using medium resolution density information coupled to comparatively large structural transitions. Practical considerations for probing the transitions between multiple intermediate density states are also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Petrology, Geochemistry, and Pairing of Lunar Meteorites from the Dominion Range

Introduction: During the 2018-2019 Antarctic Search for Meteorites (ANSMET) field season in the Dominion Range (DOM), 7 lunar meteorite stones were collected: DOM 18242 (15.1 g), DOM 18244 (25.1 g), DOM 18262 (6.8 g), DOM 18509 (16.5 g), DOM 18543 (13.6 g), DOM 18666 (45.9 g), and DOM 18678 (11.6 g). Here we present the initial results of electron microprobe and X-ray computed tomography (XCT) studies of these stones and look at the details of their petrography and mineral chemistry, as well as investigate possible pairing relationships, both with each other and with previously described lunar meteorites. Most of the work presented here is on the DOM 18509, 18543, and 18678 stones; subsamples of the other stones are in hand and similar measurements will be made on them by the time of the meeting. Methods: Textures in DOM 18509, DOM 18543, and DOM 18678 were characterized in 2D by optical microscopy, backscattered electron (BSE) imaging and elemental X-ray images on thin sections, as well as in 3D by X-ray computed tomography (XCT) on sample chips. Mineral compositions were assessed through a combination of wavelength dispersive spectroscopy EPMA (electron probe microanalysis) and x-ray mapping on the JEOL 8530 at NASA JSC. The bulk composition of all three meteorites was determined based on analyses of the fusion crust glass. XCT analyses were done on the Nikon XTH 320 at NASA JSC. ICP-MS data on bulk rock subsamples for each meteorite will be carried out in the near future. Results: The stones are all similar in macroscopic appearance with a dark aphanitic matrix hosting a variety of small- to medium-sized angular mineral and lithic fragments (often light colored in nature) [1,2]. Based on EPMA and XCT results, the three meteorites are polymict regolith breccias comprised of mineral, glass, and lithic clasts ranging up to several mm in length. Melt veins run through all three meteorite samples. Mineral clasts in all 3 stones are dominated by pyroxene and plagioclase (An82-96), with minor amounts of SiO2, olivine (Fo1-52), and FeTi-oxides. Pyroxene grains are mostly Fe-rich pigeonite and augite, and larger clasts are normally zoned and have fine exsolution lamellae. The lithic clasts in all stones consists of: (1) basalt clasts that contain zoned pyroxene, plagioclase laths, and ilmenite, with minor silica and Fe-rich olivine; (2) granulitic clasts; (3) anorthosite clasts; (4) Si-rich clasts that also contain ilmenite, troilite, high-Ca pyroxene, fayalite, and K-feldspar likely mesostasis from late stage basalts). All three meteorites contain glassy fusion crust that is highly vesicular, high in FeO and Al2O3 (15-17 wt% each), ferroan (Mg# of 23-24), and moderately rich in TiO2 (1.4-1.8 wt%). The composition of the fusion crust can serve as a proxy for the bulk meteorite composition and is identical within error for all three meteorites. Implications: The lithic and mineral clasts in all three stones are similar in clast population and assemblages as well as mineral chemistry. In addition, the fusion crust composition, a proxy for bulk composition, is within error of each other for all three stones. Thus DOM 18509, DOM 18543, and DOM 18678 are almost certainly paired. Based on similarities in macroscopic description as well as preliminary classification data [1,2], all 7 lunar stones from DOM are likely paired, though additional quantitative analyses are needed to confirm this. The presence of spherules and vesicular fusion crusts indicates that the DOM pairing group is a regolith breccia. The presence of basaltic and gabbroic clasts as well as more feldspathic materials, suggest that the regolith from which these meteorites formed contained a mixture of feldspathic highland material and mare material, suggesting a possible provenance near a marehighlands boundary. No evidence of KREEPy lithologies have been observed so far in these meteorites, however, future ICP-MS data on bulk rock chips for the stones will reveal any KREEP component if present. The DOM pairing group has many similarities to previously described lunar breccia meteorite MET 01210, however more detailed compositional data will be needed to make a definitive comparison.

R.A. Zeigler↗

Benchmarking DFT Accuracy in Predicting O 1s Binding Energies on Metals

X-ray photoelectron spectroscopy (XPS) is a powerful tool for probing the electronic structure and composition of materials, particularly metals and metal oxides of relevance to solar cells and catalysis. Density functional theory (DFT) is often used to support XPS peak assignments, but its reliability for predicting oxygen species is not well established. Here, we compile a large data set of experimental oxygen binding energies and evaluate corresponding DFT predictions. We find that as the binding energies of metal-bound atomic oxygen species increase, especially above ≈530 eV, there is a general decrease in the accuracy of DFTpredicted values. Thus, high-binding-energy atomic oxygen species, such as those proposed as active for selective Ag-catalyzed epoxidation, are less well represented. The chemical nature of the oxygen species also influences accuracy, with molecularly bound species more reliably captured across the entire range of energies. These findings illustrate the limitations of DFT for interpreting XPS spectra and provide a benchmark for improving computational methods.

Adsorption↗

The study of 'microsurfaces' using thermal desorption spectroscopy

The use of a newly combined ultrahigh vacuum technique for studying continuous and particulate evaporated thin films using thermal desorption spectroscopy (TDS), transmission electron microscopy (TEM), and transmission electron diffraction (TED) is discussed. It is shown that (1) CO thermal desorption energies of epitaxially deposited (111) Ni and (111) Pd surfaces agree perfectly with previously published data on bulk (111) single crystal, (2) contamination and surface structural differences can be detected using TDS as a surface probe and TEM as a complementary technique, and (3) CO desorption signals from deposited metal coverages of one-thousandth of a monolayer should be detectable. These results indicate that the chemisorption properties of supported 'microsurfaces' of metals can now be investigated with very high sensitivity. The combined use of TDS and TEM-TED experimental methods is a very powerful technique for fundamental studies in basic thin film physics and in catalysis.

Thomas, M. E.↗

Probing the Electronic Structure of a Thorium Nitride Complex by Solid-State 15N NMR Spectroscopy

The solid-state 15N NMR powder spectra of the thorium nitride complex, [K(18-crown-6)(THF)2][(R2N)3Th(m-15N)(Th(NR2)3] ([K][1-15N], R = SiMe3), and the thorium amide complex, [Th(NR2)3(15NH2)] (2-15N) were recorded. The spectrum for [K][1-15N] represents the first reported solid-state 15N NMR data for an actinide nitride complex. The experimentally measured tensor spans are 847 ppm for [K][1-15N] and 237 ppm for 2-15N. Both shielding tensors exhibit a near-zero asymmetry parameter, which for [K][1-15N] is consistent with a local rotational symmetry of its 15N-labelled nitride ligand. For 2-15N, the lack of asymmetry can be rationalized by a quasi-free Th-NH2 bond rotation in the solid-state. DFT calculations overestimate the tensor span somewhat for [K][1-15N], but provide isotropic shifts in good agreement with both the solid-state and solution values for both complexes. Natural localized molecular orbital (NLMO) analyses of the nuclear shielding reveal that the larger tensor span in [K][1-15N] vs. 2-15N is primarily a consequence of more pronounced covalency of the N-Th bonds, and large spin-orbit coupling due to significant Th 5f orbital contribution to those bonds, impacting the principal components of the shielding tensor perpendicular to the Th-N-Th axis. Overall, our analysis confirms the involvement of the 5f orbitals in Th-N multiple bonds, and further demonstrates the value of solid-state NMR spectroscopy for interrogating actinide-ligand bonding.

actinides, covalent bonding, Nuclear Magnetic Reso↗