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Local Structure and Short-Range Order in a NiCoCr Solid Solution Alloy

Multi-element solid solution alloys are intrinsically disordered on the atomic scale, and many of their advanced properties originate from the unique local structural characteristics. We measured the local structure of a NiCoCr solid solution alloy with X-ray/neutron total scattering and extended X-ray absorption fine structure (EXAFS) techniques. The atomic pair distribution function analysis (PDF) did not exhibit distinct structural distortion. But, EXAFS analysis suggested that the Cr atoms are favorably bonded with Ni and Co in the solid solution alloys. This short-range order (SRO) plays a role in the distinct low values of electrical and thermal conductivities in Ni-based solid solution alloys when Cr is incorporated. Both the long-range and local structures of the NiCoCr alloy upon Ni ion irradiation were studied and an irradiation-induced enhancement of SRO was found.

36 MATERIALS SCIENCE↗

Frustrated Structural Instability in Superconducting Quasi-One-Dimensional K 2 Cr 3 As 3

We present density functional theory and neutron total scattering studies on quasi-one-dimensional superconducting K 2 Cr 3 As 3 revealing a frustrated structural instability. Our first principles calculations find a significant phonon instability, which, under energy minimization, corresponds to a frustrated orthorhombic distortion. In neutron diffraction studies we find large atomic displacement parameters with anomalous temperature dependencies, which result from highly localized orthorhombic distortions of the CrAs sublattice and coupled K displacements. Furthermore, these results suggest a more complex phase diagram than previously assumed for K 2 Cr 3 As 3 with subtle interplays of structure, electron-phonon, and magnetic interactions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Oxygen point defect accumulation in single-phase U O 2 + x

UO 2.07 was characterized using neutron total scattering in order to elucidate defect morphology in the low oxygen-to-metal regime (x < 0.125 for UO 2+x ). Data were collected at temperatures (600 and 1000 °C) coinciding with the single-phase UO 2+x region of the established phase diagram, and results were compared with data of stoichiometric UO 2 collected at near-identical temperatures. Experimental data were modeled and interpreted using a holistic approach employing a combination of analyses that characterized multiple spatial length scales. Preferential modeling of long-range atomic arrangements with Rietveld refinement suggests the existence of primarily monointerstitials in UO 2.07 , whereas preferential modeling of short-range atomic structures with small-box pair distribution function (PDF) refinement indicates the presence of defect clusters in UO 2.07 . Simultaneous modeling of multiple length scales using complementary reverse Monte Carlo (RMC) and molecular dynamics (MD) methods confirms that excess oxygen atoms in UO 2.07 exist as small defects, such as monointerstitials and di-interstitials. RMC and MD results agree with diffraction analysis but differ significantly from small-box PDF refinements, which may be related to a lack of intermediate- and long-range structural information gained from the small-box PDF refinement procedure. Employing a combination of analysis methods with varying length-scale sensitivities enabled more accurate assessment of the UO 2+x defect structure. Furthermore, our findings provide experimental support for previously predicted di-interstitial defect morphologies in UO 2+x that highly influence the accurate prediction of bulk physiochemical properties of UO 2+x , such as oxygen diffusivity.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Defect Structure in Quantum-Cutting Yb3+-Doped CsPbCl3 Perovskites Probed by X-Ray Absorption and Atomic Pair Distribution Function Analysis

Ytterbium-doping in all-inorganic lead-halide perovskites (CsPb(Cl1-xBrx)3) generates novel properties including quantum cutting and narrow line emission, making these materials attractive spectral down-converters for solar photovoltaics. The relationship between this optical efficiency and the defect structure(s) associated with Yb3+ dopants within perovskites is not well understood. Various charge-neutral doping motifs have previously been proposed and studied computationally, including clusters involving two substitutional Yb3+ ions charge-compensated by a single local Pb2+ vacancy. Near-band-edge defect states associated with such motifs are believed to play an important mechanistic role in quantum cutting itself. Here, we report the results of X-ray absorption and X-ray total-scattering measurements on ytterbium-doped CsPbCl3. XANES shows that the dopant oxidation state is exclusively Yb3+, and a combination of Yb L3 and Pb L3 EXAFS shows that this Yb3+ substitutes exclusively at Pb2+ sites, where it adopts a pseudo-octahedral [YbCl6]3- coordination environment. Shell-by-shell fits to the data show a short Yb-Cl bond distance of 2.58 Å compared to the Pb-Cl bond distance of 2.83 Å. We confirm this finding by X-ray pair distribution function analysis, which also shows evidence of additional Pb2+ vacancy formation induced by Yb3+ doping. We evaluate whether this is the primary mechanism of charge compensation using simulated EXAFS and pair distribution function data for several computed defect structures. Together, these results resolve the local dopant structures and charge-compensation mechanisms in lanthanide-doped all-inorganic lead-halide perovskites, and, as such, significantly advance the understanding of structure-function relationships in this important class of materials.

Kluherz, Kyle (ORCID:0000000279865167)↗

Resolving the Solvation Structure and Transport Properties of Aqueous Zinc Electrolytes from Salt-in-Water to Water-in-Salt Using Neural Network Potential

Zn Cl 2 solutions are promising electrolytes for aqueous zinc-ion batteries. Here, we report a joint computational and experimental study of the structural and dynamic properties of aqueous Zn Cl 2 electrolytes with concentrations ranging from salt-in-water to water-in-salt (WIS). By developing a neural network potential (NNP) model, we perform molecular dynamics (MD) simulations with accuracy but at much larger lengths and longer timescales. The NNP predicted structures are validated by the structure factors measured by X-ray total scattering experiments. The MD trajectories provide a comprehensive and quantitative picture of the Zn 2 + solvation shell structures. Additionally, we find that the O − H covalent bonds in water are strengthened with increasing salt concentration, thus expanding the electrochemical stability window of aqueous electrolytes. In terms of dynamic properties, the calculated and experimentally measured conductivities are in good agreement. Through the analysis of the calculated cation transference number, we propose a three-stage charge carrier transport mechanism with increasing concentration: independent ion transport, strongly correlated ion transport, and small positive charge carrier diffusion through negatively charged polymeric clusters. Our study provides fundamental atomic scale insights into the structure and transport properties of the Zn Cl 2 electrolyte that can aid the optimization and development of WIS electrolytes. Published by the American Physical Society 2025

25 ENERGY STORAGE↗

Structure analysis of supported disordered molybdenum oxides using pair distribution function analysis and automated cluster modelling

Molybdenum oxides and sulfides on various low-cost high-surface-area supports are excellent catalysts for several industrially relevant reactions. The surface layer structure of these materials is, however, difficult to characterize due to small and disordered MoO x domains. Here, it is shown how X-ray total scattering can be applied to gain insights into the structure through differential pair distribution function (d-PDF) analysis, where the scattering signal from the support material is subtracted to obtain structural information on the supported structure. MoO x catalysts supported on alumina nanoparticles and on zeolites are investigated, and it is shown that the structure of the hydrated molybdenum oxide layer is closely related to that of disordered and polydisperse polyoxometalates. By analysing the PDFs with a large number of automatically generated cluster structures, which are constructed in an iterative manner from known polyoxometalate clusters, information is derived on the structural motifs in supported MoO x .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In situ high-temperature X-ray diffraction study of Sc-doped titanium oxide nanocrystallites

Titanium dioxide is an inexpensive wide-gap highly ionic semiconductor with striking photocatalytic capabilities in several heterogeneous photoredox reactions. A small crystal size is desirable to maximize the surface area, since photocatalytic reactions occur at the surface of a photocatalyst. Presented in this work are the synthesis and microstructural characterization of 4 at.% Sc-doped TiO 2 (4SDT) prepared by water-based co-precipitation. The crystal structure of 4SDT was examined via in situ high-temperature powder X-ray diffraction experiments from 25 to 1200°C. Rietveld analysis revealed single-phase anatase up to 875°C, while at 900°C the anatase-to-rutile phase transformation occurred and at higher temperatures additional reflections of Sc-rich phases (Sc 2 TiO 5 from 975°C and Ti 3 Sc 4 O 12 or Sc 2 O 3 at 1200°C) were observed. Debye function analysis (DFA) was applied to model the total scattering pattern directly in reciprocal space, allowing the reconstruction of Ti vacancies. Both Rietveld and DFA methods were applied to estimate the nanocrystallite size and shape with consistent growth in crystallite size with temperature: an ellipsoid shape with equatorial ~4.7 nm / axial (001) ~6.9 nm at 25°C to equatorial ~27.9 nm / axial (001) ~39.6 nm at 900°C refined by Rietveld analysis, versus a cylinder shape with D a , b = 4.3 nm and size dispersion σ ab = 1.5 nm, L c = 4.9 nm and σ c = 2.3 nm at 25°C to D a , b = 21.4 nm, σ ab = 8.3 nm, L c = 23.9 and σ c = 10.9 nm at 900°C estimated by DFA. The microstructural changes obtained by Rietveld and DFA methods were supported by high-resolution transmission electron microscopy image analysis, as well as by the less direct nitrogen sorption techniques that provide information on the size of non-agglomerated and dense particles. The Ti site-occupancy factor showed a linear increase from 0.6–0.8 at 25°C to unity at 900°C for anatase, and from ~0.7 at 900°C to unity at 1200°C for rutile, via Rietveld analysis and DFA.

36 MATERIALS SCIENCE↗

Pair distribution function analysis of nano-object assemblies

The atomic pair distribution function (aPDF) analysis technique, also known as the total scattering method, which considers both Bragg and diffuse scattering, has been used extensively to probe local atomic arrangements in crystalline and disordered materials. In contrast, there have been limited applications of the PDF in self-assembled nanomaterials, which represent a class of materials built from nanoscale objects, such as nano-colloids, micelles and proteins. As distinguished from atoms, nano-objects have polydispersity in size and shape, and such form-factor effects complicate the application of PDF analysis to nano-systems. Here, in this paper, the application of the PDF is extended to spherical nano-object assemblies and the formulae for the nano-PDF (nPDF) are derived, showing some differences from the aPDF. By numerical simulations, the properties of the nPDF (peak broadening and pattern profile) are studied systematically as a function of structural features, such as nano-object parameters (size and size polydispersity) and assembly structural features (size, shape, structure type and lattice disorder), and of data processing parameters ( q cut-off and `missing' data in ultra-small-angle regions). The nPDF analysis method is found to provide an effective route to revealing not only nanoscale but also mesoscale structural properties, for example the morphology of a nano-assembly.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

RMCProfile7 : reverse Monte Carlo for multiphase systems

This work introduces a completely rewritten version of the programRMCProfile(version 7), big-box, reverse Monte Carlo modelling software for analysis of total scattering data. The major new feature ofRMCProfile7is the ability to refine multiple phases simultaneously, which is relevant for many current research areas such as energy materials, catalysis and engineering. Other new features include improved support for molecular potentials and rigid-body refinements, as well as multiple different data sets. An empirical resolution correction and calculation of the pair distribution function as a back-Fourier transform are now also available.RMCProfile7is freely available for download at https://rmcprofile.ornl.gov/.

Chemistry↗

Atomic pair distribution function at the Brazilian Synchrotron Light Laboratory: application to the Pb 1– x La x Zr 0.40 Ti 0.60 O 3 ferroelectric system

This work reports the setting up of the X-ray diffraction and spectroscopy beamline at the Brazilian Synchrotron Light Laboratory for performing total scattering experiments to be analyzed by atomic pair distribution function (PDF) studies. The results of a PDF refinement for Al 2 O 3 standard are presented and compared with data acquired at a beamline of the Advanced Photon Source, where it is common to perform this type of experiment. A preliminary characterization of the Pb 1– x La x Zr 0.40 Ti 0.60 O 3 ferroelectric system, with x = 0.11, 0.12 and 0.15, is also shown.

Saleta, M. E.↗

Model-free reconstruction of magnetic correlations in frustrated magnets

Frustrated magnetic systems exhibit extraordinary physical properties, but quantification of their magnetic correlations poses a serious challenge to experiment and theory. Current insight into frustrated magnetic correlations relies on modelling techniques such as reverse Monte-Carlo methods, which require knowledge about the exact ordered atomic structure. Here, we present a method for direct reconstruction of magnetic correlations in frustrated magnets by three-dimensional difference pair distribution function analysis of neutron total scattering data. The methodology is applied to the disordered frustrated magnet bixbyite, (Mn 1– x Fe x ) 2 O 3 , which reveals nearest-neighbor antiferromagnetic correlations for the metal sites up to a range of approximately 15 Å. Pertinently, this technique allows for magnetic correlations to be determined directly from the experimental data without any assumption about the atomic structure.

36 MATERIALS SCIENCE↗

Background optimization of powder electron diffraction for implementation of the e-PDF technique and study of the local structure of iron oxide nanocrystals

The local structural characterization of iron oxide nanoparticles is explored using a total scattering analysis method known as pair distribution function (PDF) (also known as reduced density function) analysis. The PDF profiles are derived from background-corrected powder electron diffraction patterns (the e-PDF technique). Due to the strong Coulombic interaction between the electron beam and the sample, electron diffraction generally leads to multiple scattering, causing redistribution of intensities towards higher scattering angles and an increased background in the diffraction profile. In addition to this, the electron–specimen interaction gives rise to an undesirable inelastic scattering signal that contributes primarily to the background. The present work demonstrates the efficacy of a pre-treatment of the underlying complex background function, which is a combination of both incoherent multiple and inelastic scatterings that cannot be identical for different electron beam energies. Therefore, two different background subtraction approaches are proposed for the electron diffraction patterns acquired at 80 kV and 300 kV beam energies. From the least-square refinement (small-box modelling), both approaches are found to be very promising, leading to a successful implementation of the e-PDF technique to study the local structure of the considered nanomaterial.

36 MATERIALS SCIENCE↗

Structural Evolution in Hollandite Solid Solutions Across the A‐Site Compositional Range from Ba 1.33 Ga 2.66 Ti 5.34 O 16 to Cs 1.33 Ga 1.33 Ti 6.67 O 16

Hollandite solid solutions along the A‐site compositional range from the pure barium end‐member Ba 1.33 Ga 2.66 Ti 5.34 O 16 to the pure cesium end‐member Cs 1.33 Ga 1.33 Ti 6.67 O 16 have been synthesized using a solid‐state reaction technique. The crystal structure of the hollandite across the entire compositional range remained in the I 4 /m space group. Structural evolution was resolved by neutron diffraction, total scattering data, and density functional theory calculations. A trend of decreasing thermodynamic stability with smaller tunnel cations was attributed to increased structural distortion observed in the system. In addition, the tunnel cations' local environment was studied in the eightfold coordinated oxygen cavities. Local binding features of the tunnel cations reveals that the hollandite structure can strongly stabilize tunnel cations, even at elevated temperatures up to 500 K.

Xu, Yun↗

Effect of dosimeter type for commissioning small photon beams on calculated dose distribution in stereotactic radiosurgery

Purpose: To assess the impact of the detector used to commission small photon beams on the calculated dose distribution in stereotactic radiosurgery (SRS). Methods: In this study, six types of detectors were used to characterize small photon beams: three diodes [a silicon stereotactic field diode SFD, a silicon diode SRS, and a silicon diode E], an ionization chamber CC01, and two types of radiochromic film models EBT and EBT2. These detectors were used to characterize circular collimated beams that were generated by a Novalis linear accelerator. This study was conducted in two parts. First, the following dosimetric data, which are of particular interest in SRS, were compared for the different detectors: the total scatter factor (TSF), the tissue phantom ratios (TPRs), and the off-axis ratios (OARs). Second, the commissioned data sets were incorporated into the treatment planning system (TPS) to compare the calculated dose distributions and the dose volume histograms (DVHs) that were obtained using the different detectors. Results: The TSFs data measured by all of the detectors were in good agreement with each other within the respective statistical uncertainties: two exceptions, where the data were systematically below those obtained for the other detectors, were the CC01 results for all of the circular collimators and the EBT2 film results for circular collimators with diameters below 10.0 mm. The OAR results obtained for all of the detectors were in excellent agreement for all of the circular collimators. This observation was supported by the gamma-index test. The largest difference in the TPR data was found for the 4.0 mm circular collimator, followed by the 10.0 and 20.0 mm circular collimators. The results for the calculated dose distributions showed that all of the detectors passed the gamma-index test at 100% for the 3 mm/3% criteria. The aforementioned observation was true regardless of the size of the calculation grid for all of the circular collimators. Finally, the dose volume histogram results were independent of the size of the calculation grid used. Conclusions: The results of this study showed that all of the studied detectors produced similar commissioned data sets for the TPS dose calculations. However, this result only validated the dose distribution calculation in the TPS and could not be used to assess the dose delivery to the target in which the TFS data were used to calculate the monitor units (the TFS data were not used in the TPS dose distribution calculation). Therefore, this study could not be used to determine the most accurate detector commissioning data set; however, all of the detectors exhibited superior performance for the relative dosimetry of small photon beams.

07 ISOTOPE AND RADIATION SOURCES↗

SU-E-T-414: Experimental Correction of High-Z Electrode Effect in Mini-Ionization Chambers for Small Beam Dosimetry

Purpose: To correct for the over-response of mini-ionization chambers with high-Z central electrodes. The hypothesis is that by applying a negative/reverse voltage, it is possible to suppress the signal generated in the high-Z central electrode by low-energy photons. Methods: The mini-ionization chambers used in the experiments were a PTW-31014, PTW-31006 and IBA-CC01. The PTW-31014 has an aluminum central electrode while the PTW-31006 and IBA-CC01 have a steel one. Total scatter factors (Scp) were measured for a 6 MV photon beam down to a square field size of 0.5 cm. The measurements were performed in water at 10 cm depth with SAD of 100 cm. The Scp were measured with the dosimeters with +400V bias voltage. In the case of the PTW-31006 and IBA-CC01, the measurements were repeated with −400V bias voltage. Also, the field factors in water were calculated with Monte Carlo simulations for comparison. Results: The measured Scp at +400V with the PTW-31006 and IBA-CC01 detectors were in agreement within 0.2% down to a field size of 1.5 cm. Both dosimeters shown a systematic difference about 2.5% with the Scp measured with the PTW-31014 and the Monte Carlo calculated field factors. The measured Scp at −400V with the PTW-31006 and IBA-CC01 detectors were in close agreement with the PTW-31014 measured Scp and the field factors within 0.3 and 1.0%, respectively. In the case of the IBA-CC01 it was found a good agreement (1%) down to field size of 1.0 cm. All the dosimeters shown differences up to 17% between the measured Scp and the field factor for the 0.5 cm field size. Conclusion: By applying a negative/reverse voltage to the mini-ionization chambers with high-Z central electrode it was possible to correct for their over-response to low energy photons.

07 ISOTOPE AND RADIATION SOURCES↗

SU-E-T-597: Parameterization of the Photon Beam Dosimetry for a Commercial Linear Accelerator

Purpose: In radiation therapy, accurate data acquisition of photon beam dosimetric quantities is important for (1) beam modeling data input into a treatment planning system (TPS), (2) comparing measured and TPS modelled data, (3) a linear accelerator’s (linac) beam characteristics quality assurance process, and (4) establishing a standard data set for data comparison, etcetera. Parameterization of the photon beam dosimetry creates a portable data set that is easy to implement for different applications such as those previously mentioned. The aim of this study is to develop methods to parameterize photon percentage depth doses(PDD), profiles, and total scatter output factors(Scp). Methods: Scp, PDDs and profiles for different field sizes (from 2×2 to 40×40cm{sup 2}), depths and energies were measured in a linac using a three-dimensional water tank. All data were smoothed and profile data were also centered, symmetrized and geometrically scaled. The Scp and PDD data were analyzed using exponential functions. For modelling of open and wedge field profiles, each side was divided into three regions described by exponential, sigmoid and Gaussian equations. The model’s equations were chosen based on the physical principles described by these dosimetric quantities. The equations’ parameters were determined using a least square optimization method with the minimal amount of measured data necessary. The model’s accuracy was then evaluated via the calculation of absolute differences and distance–to–agreement analysis in low gradient and high gradient regions, respectively. Results: All differences in the PDDs’ buildup and the profiles’ penumbra regions were less than 2 mm and 0.5 mm, respectively. Differences in the low gradient regions were 0.20 ± 0.20% and 0.50 ± 0.35% for PDDs and profiles, respectively. For Scp data, all differences were less than 0.5%. Conclusion: This novel analytical model with minimum measurement requirements proved to accurately calculate PDDs, profiles, and Scp for different field sizes, depths and energies.

61 RADIATION PROTECTION AND DOSIMETRY↗

Parameterization of photon beam dosimetry for a linear accelerator

Purpose: In radiation therapy, accurate data acquisition of photon beam dosimetric quantities is important for (1) beam modeling data input into a treatment planning system (TPS), (2) comparing measured and TPS modeled data, (3) the quality assurance process of a linear accelerator’s (Linac) beam characteristics, (4) the establishment of a standard data set for comparison with other data, etcetera. Parameterization of the photon beam dosimetry creates a data set that is portable and easy to implement for different applications such as those previously mentioned. The aim of this study is to develop methods to parameterize photon beam dosimetric quantities, including percentage depth doses (PDDs), profiles, and total scatter output factors (S{sub cp}). Methods: S{sub cp}, PDDs, and profiles for different field sizes, depths, and energies were measured for a Linac using a cylindrical 3D water scanning system. All data were smoothed for the analysis and profile data were also centered, symmetrized, and geometrically scaled. The S{sub cp} data were analyzed using an exponential function. The inverse square factor was removed from the PDD data before modeling and the data were subsequently analyzed using exponential functions. For profile modeling, one halfside of the profile was divided into three regions described by exponential, sigmoid, and Gaussian equations. All of the analytical functions are field size, energy, depth, and, in the case of profiles, scan direction specific. The model’s parameters were determined using the minimal amount of measured data necessary. The model’s accuracy was evaluated via the calculation of absolute differences between the measured (processed) and calculated data in low gradient regions and distance-to-agreement analysis in high gradient regions. Finally, the results of dosimetric quantities obtained by the fitted models for a different machine were also assessed. Results: All of the differences in the PDDs’ buildup and the profiles’ penumbra regions were less than 2 and 0.5 mm, respectively. The differences in the low gradient regions were 0.20% ± 0.20% (<1% for all) and 0.50% ± 0.35% (<1% for all) for PDDs and profiles, respectively. For S{sub cp} data, all of the absolute differences were less than 0.5%. Conclusions: This novel analytical model with minimum measurement requirements was proved to accurately calculate PDDs, profiles, and S{sub cp} for different field sizes, depths, and energies.

61 RADIATION PROTECTION AND DOSIMETRY↗