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Spin dynamics and exchange interaction in orthoferrite TbFeO 3 with non-Kramers rare-earth ion

The low-temperature spin dynamics of the orthorhombic TbFeO 3 perovskite has been studied. It has been found that the inelastic neutron scattering (INS) spectrum of the investigated compound contains two modes corresponding to different sublattices. It is shown that the iron subsystem orders antiferromagnetically at T N =632 K and exhibits the high-energy magnon dispersion. The magnetic dynamics of this subsystem has been described within the linear spin wave theory and the in-plane and out-of-plane exchange anisotropy has been demonstrated. The approach proposed previously to describe the magnon dispersion in the TmFeO 3 compound has been used. Three levels of the nondispersive crystal electric field corresponding to Tb 3+ ions have been found in the energy region below 40 meV at about 17, 26, and 35 meV. The behavior of the magnetic correlation length of the terbium subsystem has been determined by studying the diffuse scattering at different temperatures. The evolution of this subsystem has been numerically described within the point charge model. In conclusion, it is shown that the numerical data agree satisfactorily with the experiment and with the general concept of the single-ion approximation applied to the rare-earth subsystem of orthorhombic perovskites.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural Properties of [N1888][TFSI] Ionic Liquid: A Small Angle Neutron Scattering and Polarizable Molecular Dynamics Study

In this study, we investigate the quaternary ammonium-based ionic liquid (QAIL), methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, [N 1888 ][TFSI], utilizing small angle neutron scattering (SANS) measurements and polarizable molecular dynamics (MD) simulations to characterize the shortand long-range liquid structure. Scattering structure factors show signatures of three length scales in reciprocal space indicative of alternating polarity (k ~ 0.44 Å –1 ), charge (k ~ 0.75 Å –1 ), and neighboring or adjacent (k ~ 1.46 Å –1 ) domains. Excellent agreement between simulation and experimental scattering structure factors validates various simulation analyses that provide detailed atomistic characterization of the different length scale correlations. The first solvation shell structure is illustrated by obtaining radial, angular, dihedral, and combined distribution functions, where two dominant spatial motifs, N + ···N – and N + ···O – , compete for optimal packing around the polar head of the [N 1888 ] + cation. Intermediate and long-range structures are governed by the balance between local electroneutrality and octyl chain networking, respectively. By computing the charge-correlation structure factor, S ZZ , and the spatial extent of the octyl chain network using graph theory, the bulk-phase structure of [N 1888 ][TFSI] is characterized in terms of electrostatic screening and apolar domain formation length scales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deciphering Photoinduced Catalytic Reaction Mechanisms in Natural and Artificial Photosynthetic Systems on Multiple Temporal and Spatial Scales Using X-ray Probes

Utilization of renewable energies for catalytically generating value-added chemicals is highly desirable in this era of rising energy demands and climate change impacts. Artificial photosynthetic systems or photocatalysts utilize light to convert abundant CO 2 , H 2 O, and O 2 to fuels, such as carbohydrates and hydrogen, thus converting light energy to storable chemical resources. Here, the emergence of intense X-ray pulses from synchrotrons, ultrafast X-ray pulses from X-ray free electron lasers, and table-top laser-driven sources over the past decades opens new frontiers in deciphering photoinduced catalytic reaction mechanisms on the multiple temporal and spatial scales. Operando X-ray spectroscopic methods offer a new set of electronic transitions in probing the oxidation states, coordinating geometry, and spin states of the metal catalytic center and photosensitizers with unprecedented energy and time resolution. Operando X-ray scattering methods enable previously elusive reaction steps to be characterized on different length scales and time scales. The methodological progress and their application examples collected in this review will offer a glimpse into the accomplishments and current state in deciphering reaction mechanisms for both natural and synthetic systems. Looking forward, there are still many challenges and opportunities at the frontier of catalytic research that will require further advancement of the characterization techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Graft copolymers from poly(2,6-dimethylphenylene oxide) and pivalolactone

The copolyether-polyester system resulting from the anionic graft polymerization of pivalolactone onto poly(2,6-dimethylphenylene oxide) has been formulated with differing graft densities and graft segment lengths. Wide angle X-ray scattering studies on these materials indicated an increased crystalline order with increased PVL segments/graft for similarly annealed specimens and a decrease in such order with increasing carboxylation.

Bell, Vernon L.↗

In situ electric field X-ray total scattering reveals composition-dependent electromechanical strain mechanisms in (1 − x )BiFe 2/8 Ti 3/8 Mg 3/8 O 3 – x PbTiO 3 ceramics

Ferroelectric materials find many applications in energy and aerospace industries. A major challenge for ferroelectric materials is maintaining their properties at elevated temperatures. The (1 − x )BiFe 2/8 Ti 3/8 Mg 3/8 O 3 – x PbTiO 3 (BFTM–xPT) ferroelectric solid solution is a promising candidate for high-temperature applications as it has a high piezoelectric response while also maintaining its ferroelectric phase until a high Curie temperature (T C ) of 650 °C. In this work, we investigate the piezoelectric mechanism in BFTM–xPT, a novel high-T C ferroelectric ceramic. To elucidate the origin of its enhanced piezoelectric performance, relative to other piezoceramics of similar T C , in situ electric field X-ray total scattering experiments were performed. Total scattering combines Bragg scattering (diffraction) and diffuse scattering (pair distribution function), providing insight on various length scales. With information spanning different length scales, extrinsic contributions (i.e., domain wall motion and interphase boundary motion) can be separated from intrinsic contributions (i.e., piezoelectric lattice strain). We show that, for compositions within the morphotropic phase boundary (MPB, x = 0.325), the piezoelectric response is dominated by intrinsic piezoelectric lattice strain, whereas outside the MPB (x = 0.375) the major component of the piezoelectric response is from extrinsic mechanisms including an electric-field-induced phase transition and tetragonal domain wall motion. This article reveals that the origin of piezoelectric response in BFTM–xPT is composition-dependent and shows that high-performance materials may also be located outside the MPB. These findings can help guide material design to optimize properties for specific applications.

Richtik, Brooke N. [University of Calgary, AB (Can↗

Thermocouple Testing in Support of the AGR-5/6/7 Experiment

This report documents thermocouple testing performed in IRC Lab C-15 over a period of seven years. This testing supported selection and characterization of the thermocouple set used in the AGR-5/6/7 experiment. The following summary was taken directly from the report. Temperature measurement is a challenging aspect of very high temperature irradiation experiments because commonly used high-temperature commercial thermocouples such as platinum-rhodium (Types S, R, and B) and tungsten-rhenium (Type C), suffer dramatic drift because of neutron-induced transmutation. As a result, these types of thermocouples, which are used routinely for industrial temperature measurements outside of reactors, are used only in very special circumstances for reactor experiments. Conversely, because of their low neutron cross-sections, Type N thermocouples are affected to only a limited extent by neutron irradiation. However, the use of these nickel-based thermocouples is limited when the temperature exceeds 1050°C due to drift arising from minor alloying elements migrating from the thermocouple's metal sheath to the thermoelements. This change in the composition of the thermo-elements results in significant decalibration of the signal. The issues described above were recognized during the early planning stages of the final AGR experiment (designated AGR-5/6/7), and a thermocouple furnace testing program was performed over a seven-year period (2014-2019, 2021) to first select and then characterize the best thermocouple set for the high temperature regions of the AGR-5/6/7 irradiation experiment. The calculated temperature range of the AGR-5/6/7 experiment was 600–1500°C. For temperatures below 1000°C standard Type N thermocouples were deemed adequate. The furnace testing campaign identified two thermocouple types suitable for measuring temperatures above 1000°C, a Mo/Nb thermocouple developed at INL called HTIR-TC, and a Type N thermocouple developed by Cambridge University (called herein Cambridge Type N), which featured a custom high nickel alloy sheath. One of the original goals of the furnace testing program was to identify a thermocouple capable of low drift operation near the peak temperature expected in AGR-5/6/7, i.e., about 1400°C. The HTIR-TC design appeared promising in this regard, however a manufacturing difficulty proved to be a barrier and instead the furnace testing focused on drift performance at 1250°C. The manufacturing difficulty was that the Nb sheaths of the HTIR-TCs experienced extreme embrittlement when heat treated at 1600°C or greater. Heat treatment is needed to stabilize the emf output of this TC type, and the higher the heat treatment temperature the higher the peak temperature of stable operation. Because of the sheath embrittlement the heat treatment temperature had to be lowered to 1450°C resulting in a stable operating temperature of about 1250°C. One of the successes of the furnace testing program was identification of a shortcoming in the heat treatment procedure that had been traditionally used in the production of HTIR-TCs. The shortcoming was that the entire heated length of the HTIR-TC sensor was not being heat treated, but rather only the part of the sensor expected to experience temperatures above 1000°C. The problem manifested itself when the thermocouples were removed from the heat treat furnace and placed in another furnace with a different geometry, their indicated temperatures would be widely scattered, but mostly in the negative direction. The solution was to heat treat the entire heated length of the sensor. Since the deepest immersion depth in the AGR-5/6/7 experiment was about 40 inches, a heat treatment length of 48 inches was used. After this change was implemented, thermocouples which were moved into a new environment with a different temperature profile (i.e., a different furnace), produced accurate temperature measurements. Although assembly of the AGR-5/6/7 experiment was completed in September of 2017 (and irradiation begun in 2018), furnace testing of thermocouples continued in 2018 and 2019. The main purpose of this testing was to establish very long-term drift characteristics of the HTIR and Cambridge Type N thermocouples installed in the experiment. Representative thermocouples from the same lots as those installed in the AGR-5/6/7 experiment were used. Additionally, thermocouples of different designs, (particularly variations on the HTIR-TC design) were "piggy-backed" on this testing program to provide insights for instrumenting future very high temperature irradiation experiments. This two-year testing program demonstrated that HTIR-TCs and Cambridge Type N TCs could operate at 1250°C for up to 10,000 hrs (and in some cases longer) while experiencing negative drifts on the order of 2-4°C/1000 hrs. This performance was considered acceptable given the extreme operating environment the sensors faced.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Hindered segmental dynamics in associative protein hydrogels studied by neutron spin-echo spectroscopy

Transient binding between associating macromolecules can cause qualitative changes to chain dynamics, including modes of conformational relaxation and diffusion, through tethering effects imparted by long-range connectivity. Here, in this work, the role of binding on short-time segmental dynamics in associative polymer gels is investigated by neutron spin-echo (NSE) measurements on a class of model artificial coiled-coil proteins with a systematically varied architecture, probing timescales of 0.1–130 ns, and length scales close to the molecular radius of gyration. The results illustrate effects of transient cross-linking on chain dynamics on different timescales, manifested in changes in segmental relaxation behavior with variations in strand length, chain concentration, and sticker distribution (endblock- vs midblock-functionalized). In all gels, a short-time cooperative diffusion mode is seen over all wave vectors, analogous to a semidilute solution, with no transitions seen at any known structural length scale. However, the diffusion coefficients are found to decrease with increasing junction density across all gels, with the strand length and number of stickers per chain in each gel appearing to play a relatively minor role. The slowing of cooperative diffusion with junction density contrasts with classical predictions of a greater restoring force for fluctuation dissipation due to the increased elasticity, suggesting additional effects of the coiled-coil junctions such as an enhancement in local viscosity that slows dynamics. Notably, the relaxation rates for all gels can be rescaled by the interjunction spacing inferred from small-angle neutron scattering, where they collapse onto a master curve suggestive of self-similar dynamics even in networks with different strand lengths and chain architectures. On long timescales (but shorter than the junction exchange time), a slowing of network relaxation is observed, resulting in a nondecaying plateau in the spin-echo amplitude attributed to a freezing of chain dynamics due to tethering. A characteristic length scale corresponding to the extent of dynamic fluctuations is estimated for each gel, which appears to be smaller than the interjunction spacing but similar to the correlation blob size of the overlapping strands. The results indicate an important role of transient binding on molecular-scale dynamics in associative polymer gels, even on timescales shorter than the junction exchange time, in addition to its effects on long-range self-diffusion previously observed.

36 MATERIALS SCIENCE↗

Influence of controlled disorder on the dipolar spin-ice state of Ho-based pyrochlores

Pyrochlore magnets of the form 𝑅 2 ⁢𝐵 2 ⁢O 7 , in which rare-earth ions on the 𝑅 site form a three-dimensional network of corner-sharing tetrahedra, provide a canonical setting for geometrical frustration. Ho-based pyrochlores host a dipolar spin-ice ground state, characterized by Ising moments constrained by the ice rules and elementary excitations analogous to magnetic monopoles. Here, in this work, we examine how controlled chemical disorder influences this state by introducing site mixing on the nonmagnetic 𝐵 site in two compounds. Ho 2⁢ GaSbO 7 contains only Ga 3+ /Sb 5+ charge disorder, whereas Ho 2 ⁢ScSbO 7 exhibits both charge and substantial size disorder arising from the large ionic-radius mismatch between Sc 3+ and Sb 5+ . Although both materials retain the pyrochlore structure, neutron-scattering measurements reveal a reduced correlation length for the 𝑅/𝐵-site cation ordering and enhanced local structural distortions in Ho 2 ⁢ScSbO 7 . Despite these structural differences, bulk thermodynamic measurements and magnetic diffuse scattering demonstrate that both systems exhibit the defining signatures of a dipolar spin-ice state. Low-energy inelastic neutron spectroscopy further uncovers broad magnetic excitations that develop within the dipolar spin-ice regime, a feature absent in pristine Ho pyrochlores and indicative of disorder-induced splitting of the non-Kramers ground-state doublet. Together, these results show that controlled disorder generates tunable transverse-field-driven quantum fluctuations in Ho-based pyrochlores, although the dipolar spin-ice state is remarkably robust to this disorder.

magnetic anisotropy↗

Electron-phonon coupling and superconductivity in the doped topological crystalline insulator ( Pb 0.5 Sn 0.5 ) 1 – x In x Te

Here, we present a neutron-scattering study of phonons in single crystals of ( Pb 0.5 Sn 0.5 ) 1 – x In x Te with x = 0 (metallic, but nonsuperconducting) and x = 0.2 (nonmetallic normal state, but superconducting). We map the phonon dispersions (more completely for x = 0 ) and find general consistency with theoretical calculations, except for the transverse and longitudinal optical (LO) modes at the Brillouin-zone center. At low temperature, both modes are strongly damped but sit at a finite energy ( ≈ 4 meV in both samples), shifting to higher energy at room temperature. These modes are soft due to a proximate structural instability driven by the sensitivity of Pb-Te and Sn-Te p -orbital hybridization to off-center displacements of the metal atoms. The impact of the soft optical modes on the low-energy acoustic modes is inferred from the low thermal conductivity, especially at low temperature. Given that the strongest electron-phonon coupling is predicted for the LO mode, which should be similar for both studied compositions, it is intriguing that only the In-doped crystal is superconducting. In addition, we observe elastic diffuse (Huang) scattering that is qualitatively explained by the difference in Pb-Te and Sn-Te bond lengths within the lattice of randomly distributed Pb and Sn sites. We also confirm the presence of anomalous diffuse low-energy atomic vibrations that we speculatively attribute to local fluctuations of individual Pb atoms between off-center sites.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantitative Prediction of Perovskite Stability Using Accelerated Testing and Machine Learning

PV technologies based on hybrid perovskites offer the potential for reducing solar cell costs, but they are particularly vulnerable to degradation by environmental factors such as moisture, oxygen, and illumination. Commercialization will require not only stable materials and device architectures but also accelerated testing protocols and models that can predict degradation from the accelerated testing data. Here, we report results from in situ photoluminescence (PL) and photoconductivity (PC) measurements during perovskite degradation with simultaneous optical transmittance (Tr) measurements or reflected dark field (DF) imaging. From PL, PC, Tr, and DF, we determine (respectively) the steady-state quasi-Fermi level splitting, the mean effective carrier diffusion length, the extent of conversion of perovskite to higher bandgap degradation products, and the extent of scattering from domains with different orientation or composition, all as a function of time during degradation. Simultaneous measurement of PL-PC-Tr or PL-PC-DF on perovskite absorbers in an environmental chamber over a wide range of humidity, oxygen, temperature, and illumination levels yields a rich data set. We use machine learning to develop a model that accurately predicts (within 10%) the time for the diffusion length to decrease to 85% of its initial value. The model takes the environmental conditions and the first few measurements from the PL-PC-Tr or PL-PC-DF experiment as input. Thus, the model provides a framework to interpret the results of accelerated testing of absorber materials. One of the dominant features in the model of degradation for CH 3 NH 3 PbI 3 is the initial rate at which transmittance increase. For devices with opaque contacts, the pixel-averaged rate of change of the intensity in dark-field images can be used in place of transmittance. Results are also presented on full PV devices with in-situ current-voltage (JV) measurements. Here, the data from simultaneous PL-DF-JV under environmental stresses reveal intimate connection between degradation and shunts and provide a framework to extend accelerated testing to devices. Further, the presentation reveals underlying universal behavior in degradation pathways over a broad range of environmental stresses and perovskite compositions.

14 SOLAR ENERGY↗

Calculating Scattering At Circular-Waveguide Junctions

Computer program calculates scattering matrices for circular waveguides including step discontinuities between collinear sections of different radii. Radius and length of each section specified arbitrarily. Examples of devices analyzed with program include waveguides with single step discontinuities, matching sections, corrugated straight sections, and corrugated horns. Sections with smooth tapers and horns with arbitrary profiles approximated by series of small steps.

Hoppe, D. J.↗

Comparative Analysis of Radial and Random Microstructures of Mesophase Pitch Carbon Fibers

Carbon fibers (CF) with radial and random microstructures are produced. Here, these fibers are subjected to identical treatment before being mechanically tested and analyzed with Weibull analysis, with the results revealing a statistically significant difference in tensile strengths of 2.23 GPa for random CF and 1.69 GPa for radial CF. Raman mapping probed the crystalline structure perpendicular to the fiber axis and found a uniform structure, while wide‐angle X‐ray diffraction showed a significant difference of 7.5 Å in the crystallites’ basal lengths parallel to the fiber. Small‐angle X‐ray scattering is completed parallel to the fiber for the first time. A cross‐section Guinier plot of the 1D azimuthal integration is generated assuming symmetric scattering, and the parallel scatterers are found to have a similar length scale to the crystallite's length, validating the testing method. Finally, transmission electron microscopy is completed on the longitudinal cross‐section of each fiber. The radial carbon fiber is found to have a core–shell structure, as evidenced further by fast Fourier transform images. Through all studies, it is shown that the structure developed during mesophase pitch spinning altered the microstructure, thus impacting the mechanical properties, confirming a direct relationship between processing, structure, and properties.

Scherschel, Alexander [Univ. of Virginia, Charlott↗

The Thomas theorem and the Efimov States within a generalized Bohr model

Using a generalized Bohr model and the hyper-spherical formalism for a three-body system, we derive the universal energy functions. We apply our model to 4He atom where only the Coulomb potential is dominant and find that its binding energy is well reproduced (less than 5.5% difference). Later, we focus on the equal mass three-body systems and derive the Thomas theorem assuming a simple interaction depending on the range of the potential. We discuss the conditions for which an unbound two-body system produces a bound three-body system and apply our model to 4He and triton atoms as well as to the triton nucleus. Using their scattering lengths and effective ranges, we are able to reproduce the two-body or the three-body binding energies (less than 5% difference) with only one parameter fitted. Prediction for excited (Efimov) levels are also given and in particular we demonstrate that for some hyper-angles two equal minima appear which indicate a phase (shape) transition similar to the Landau's theory of phase transition. We suggest that the observed excited levels in two different experiments for the triton nucleus are indeed Efimov levels and there may be more surprises.

74 ATOMIC AND MOLECULAR PHYSICS↗

Response characteristics of laser diffraction particle size analyzers - Optical sample volume extent and lens effects

The response characteristics of laser diffraction particle sizing instruments were studied theoretically and experimentally. In particular, the extent of optical sample volume and the effects of receiving lens properties were investigated in detail. The experimental work was performed with a particle size analyzer using a calibration reticle containing a two-dimensional array of opaque circular disks on a glass substrate. The calibration slide simulated the forward-scattering characteristics of a Rosin-Rammler droplet size distribution. The reticle was analyzed with collection lenses of 63 mm, 100 mm, and 300 mm focal lengths using scattering inversion software that determined best-fit Rosin-Rammler size distribution parameters. The data differed from the predicted response for the reticle by about 10 percent. A set of calibration factor for the detector elements was determined that corrected for the nonideal response of the instrument. The response of the instrument was also measured as a function of reticle position, and the results confirmed a theoretical optical sample volume model presented here.

Hirleman, E. D.↗

Different agglomeration properties of PC 61 BM and PC 71 BM in photovoltaic inks – a spin-echo SANS study

Fullerene derivatives are used in a wide range of applications including as electron acceptors in solution-processable organic photovoltaics. We report agglomeration of fullerene derivatives in optically opaque solutions of PC 61 BM and PC 71 BM, with concentrations ranging from 30 mg mL -1 up to 90 mg mL -1 , in different solvents with relevance to organic photovoltaics, using a novel neutron scattering technique, Spin-Echo Small Angle Neutron Scattering (SESANS). From SESANS, agglomerates with correlation lengths larger than 1 μm are found in some PC 61 BM solutions, in contrast no agglomerates are seen in PC 71 BM solutions. These results clearly show that PC 71 BM is fundamentally more soluble than PC 61 BM in the solvents commonly used in photovoltaic inks and corroborating similar observations previously achieved using other experimental techniques. Computer models are presented to study the energetics of solution and agglomeration of both species, ascribing the difference to a kinetic effect probably related to the larger anisotropy of PC 71 BM. Also, this work showcases the power of SESANS to probe agglomerates of fullerene derivatives in completely opaque solutions for agglomerates of the order of one to several microns.

36 MATERIALS SCIENCE↗

Fractal dimension in nonhyperbolic chaotic scattering

In chaotic scattering there is a Cantor set of input-variable values of zero Lebesgue measure (i.e., zero total length) on which the scattering function is singular. For cases where the dynamics leading to chaotic scattering is nonhyperbolic (e.g., there are Kolmogorov-Arnol'd-Moser tori), the nature of this singular set is fundamentally different from that in the hyperbolic case. In particular, for the nonhyperbolic case, although the singular set has zero total length, strong evidence is presented to show that its fractal dimension is 1.

Lau, Yun-Tung↗

Disordered quantum transport in quantum anomalous Hall insulator-superconductor junctions

In this work we numerically studied disordered quantum transport in a quantum anomalous Hall insulator-superconductor junction based on the effective edge model approach. In particular, we focus on the parameter regime with the mean-free path due to elastic scattering much smaller than the sample size and superconductor coherence length, and discuss disordered transport behavior in the presence of different numbers of chiral edge modes, as well as nonchiral metallic modes. Our numerical results demonstrate that the presence of multiple chiral edge modes or nonchiral metallic modes will lead to a strong Andreev conversion, giving rise to half-electron half-hole transmission through the junction structure, in sharp contrast to the suppression of Andreev conversion in the single chiral edge mode case. Finally, our results suggest the importance of additional transport modes in the quantum anomalous Hall insulator-superconductor junction and will guide future transport measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Backscatter RCS for TE and TM excitations of dielectric-filled cavity-backed apertures in two-dimensional bodies

Transverse electric (TE) and transverse magnetic (TM) scattering from dielectric-filled, cavity-backed apertures in two-dimensional bodies are treated using the method of moments technique to solve a set of combined-field integral equations for the equivalent induced electric and magnetic currents on the exterior of the scattering body and on the associated aperture. Results are presented for the backscatter radar cross section (RCS) versus the electrical size of the scatterer for two different dielectric-filled cavity-backed geometries. The first geometry is a circular cylinder of infinite length which has an infinite length slot aperture along one side. The cavity inside the cylinder is dielectric filled and is also of circular cross section. The two cylinders (external and internal) are of different radii and their respective longitudinal axes are parallel but not collocated. The second is a square cylinder of infinite length which has an infinite length slot aperture along one side. The cavity inside the square cylinder is dielectric-filled and is also of square cross section.

Goggans, Paul M.↗