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At least 37 records · Page 2

Unconventional magnetic order emerging from competing energy scales in the new R Rh 3 Si 7 intermetallics ( R = Gd-Yb)

The competition between Ruderman-Kittel-Kasuya-Yosida (RKKY), crystal electric field (CEF), and Kondo energy scales has recently emerged at the heart of complex magnetism in several Ce- or Yb-based intermetallics. Hard axis magnetic order has been observed in a handful of these compounds, independent of the crystal symmetry, size of the ordered moment, or the relative scale of the Kondo and magnetic ordering temperatures. This raises the question of the role of each energy scale in driving the ground state properties. In focusing on a single class of compounds, the rhombohedral RRh 3 Si 7 , we compare the anisotropy and magnetic ground states in members of this series with only RKKY interactions (R = Gd), or RKKY and CEF effects (R = Tb-Tm), with the behavior of the R = Yb compound, where all three energy scales (RKKY, CEF, Kondo) are at play. Moreover, we extend the comparison to two other isostructural Kondo systems YbIr 3 Si 7 and YbIr 3 Ge 7 , where hard axis magnetic order is also observed. The non-Kondo compounds RRh 3 Si 7 (R = Tb-Tm) lack the complexity of magnetic order along the hard CEF axis, pointing to the dominant role of the Kondo effect in driving this magnetic order. Furthermore, the CEF-RKKY competition is still responsible for complex magnetic ground states, and it appears that the electronic and magnetic degrees of freedom are entangled in all magnetic members of this series of compounds.

36 MATERIALS SCIENCE↗

DWPF Melter Off-Gas Chemistry Model for the Nitric-Glycolic Acid Flowsheet

The Defense Waste Processing Facility (DWPF) melter off-gas flammability model for the current nitricformic acid (NFA) flowsheet was revised in Revision 0 to reflect the upcoming reductant change from formic to glycolic acid. The necessary data for the model revision was obtained during Phase 2 of the Coldcap Evaluation Furnace (CEF) test, which was completed on March 21, 2014 after 24 days of round-theclock feeding and pouring, including a total downtime of ~20 hours due to equipment failures. Specifically, the CEF was run to generate steady state melter off-gas data during the first 10 days using two nitricglycolic acid (NGA) flowsheet feeds prepared at 100% and 125% acid stoichiometry from the same Sludge Batch 6 (SB6) simulant used during the Phase 1 CEF test in 2013. Each feed was fed under both bubbled and non-bubbled conditions, while maintaining the CEF vapor space temperature constant for at least two hours approximately at 700, 600, 500, 400, 350, and <300 °C for a total of 26 steady state runs. During the next 8 days, the CEF was run at the nominal vapor space temperature of 700 °C to generate the off-gas surge data using the 100% acid-stoichiometry feed under bubbled and non-bubbled conditions. The remaining days were spent on producing additional data using the 100% acid-stoichiometry feed spiked with excess antifoam as well as re-running some of the earlier steady state runs.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DWPF Melter Off-Gas Flammability Model for the Nitric-Glycolic Acid Flowsheet

The existing DWPF melter off-gas flammability model for the nitric-formic acid flowsheet feeds has been revised to reflect the upcoming reductant change from formic to glycolic acid. The necessary data for the model revision was obtained during Phase 2 of the Cold cap Evaluation Furnace (CEF) test, which was completed on March 21, 2014 after 24 days of round-the-clock feeding and pouring, including a total downtime of ~20 hours due to equipment failures. Specifically, the CEF was run to generate steady state melter off-gas data during the first 10 days using two nitric-glycolic acid flowsheet feeds prepared from a Sludge Batch 6 (SB6) simulant at 100% and 125% acid stoichiometry. Each feed was run under both bubbled and non-bubbled conditions, while maintaining the CEF vapor space temperature constant for at least two hours each targeting at 700, 600, 500, 400, 350, and <300 °C for a total of 24 steady state runs. During the next 8 days, the CEF was run at nominal vapor space temperature of 700 °C to generate off-gas surge data using the 100% acid stoichiometry feed under both bubbled and non-bubbled conditions. The remaining days were spent on producing additional steady state data using the 100% acid stoichiometry feed spiked with excess antifoam as well as re-running some of the earlier steady state runs.

CEF Phase 2↗

Alternate Reductant Cold Cap Evaluation Furnace Phase II Testing

Savannah River Remediation (SRR) conducted a Systems Engineering Evaluation (SEE) to determine the optimum alternate reductant flowsheet for the Defense Waste Processing Facility (DWPF). Specifically, two proposed flowsheets (nitric–formic–glycolic and nitric–formic–sugar) were evaluated based upon results from preliminary testing. Comparison of the two flowsheets among evaluation criteria indicated a preference towards the nitric–formic–glycolic flowsheet. Further research and development of this flowsheet eliminated the formic acid, and as a result, the nitric–glycolic flowsheet was recommended for further testing. Based on the development of a roadmap for the nitric–glycolic acid flowsheet, Waste Solidification Engineering (WS-E) issued a Technical Task Request (TTR) to address flammability issues that may impact the implementation of this flowsheet. Melter testing was requested in order to define the DWPF flammability envelope for the nitric-glycolic acid flowsheet. The Savannah River National Laboratory (SRNL) Cold Cap Evaluation Furnace (CEF), a 1/12 th scale DWPF melter, was selected by the SRR Alternate Reductant project team as the melter platform for this testing. The overall scope was divided into the following sub-tasks as discussed in the Task Technical and Quality Assurance Plan (TTQAP): Phase I - A nitric–formic acid flowsheet melter test (unbubbled) to baseline the CEF cold cap and vapor space data to the benchmark melter flammability models; Phase II - A nitric–glycolic acid flowsheet melter test (unbubbled and bubbled) to: Define new cold cap reactions and global kinetic parameters in support of the melter flammability model development; Quantify off-gas surging potential of the feed; Characterize off-gas condensate for complete organic and inorganic carbon species. After charging the CEF with cullet from Phase I CEF testing, the melter was slurry-fed with glycolic flowsheet based SB6-Frit 418 melter feed at 36% waste loading and was operated continuously for 25 days. Process data was collected throughout testing and included melter operation parameters and off-gas chemistry. In order to generate off-gas data in support of the flammability model development for the nitric-glycolic flowsheet, vapor space steady state testing in the range of ~300-750°C was conducted under the following conditions, (i) 100% (nominal and excess antifoam levels) and 125% stoichiometry feed and (ii) with and without argon bubbling. Adjustments to feed rate, heater outputs and purge air flow were necessary in order to achieve vapor space temperatures in this range. Surge testing was also completed under nominal conditions for four days with argon bubbling and one day without argon bubbling.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Diffusive excitonic bands from frustrated triangular sublattice in a singlet-ground-state system

Magnetic order in most materials occurs when magnetic ions with finite moments arrange in a particular pattern below the ordering temperature. Intriguingly, if the crystal electric field (CEF) effect results in a spin-singlet ground state, a magnetic order can still occur due to the exchange interactions between neighboring ions admixing the excited CEF levels. The magnetic excitations in such a state are spin excitons generally dispersionless in reciprocal space. Here we use neutron scattering to study stoichiometric Ni 2 Mo 3 O 8 , where Ni 2+ ions form a bipartite honeycomb lattice comprised of two triangular lattices, with ions subject to the tetrahedral and octahedral crystalline environment, respectively. We find that in both types of ions, the CEF excitations have nonmagnetic singlet ground states, yet the material has magnetic order. Furthermore, CEF spin excitons from the tetrahedral sites form a dispersive diffusive pattern around the Brillouin zone boundary, likely due to spin entanglement and geometric frustrations.

36 MATERIALS SCIENCE↗

Quenched disorder in the triangular lattice antiferromagnet YbZn 2⁢ GaO 5

We investigate the crystal electric field (CEF) excitations of Yb 3+ ions in powder samples of the triangular-lattice rare-earth-based antiferromagnet YbZn 2⁢ GaO 5 using inelastic neutron scattering (INS). Three CEF excitations from the ground-state Kramers doublet were observed, each exhibiting significant broadening beyond instrumental resolution. Combining temperature-dependent INS and neutron powder diffraction, we identify a significant static contribution to this broadening and attribute it to heterogeneous coordination of Yb 3+ ions due to Ga 3+ /Zn 2+ site mixing. Rietveld refinement of neutron powder diffraction indicates that 35% of Ga occupies the Zn site and 60% of Zn occupies the Ga site. We show with a point charge model for the CEF Hamiltonian that heterogeneous coordination of Yb3+ ions leads to broadened CEF peaks. First-principles calculations demonstrate that the random Ga 3+ /Zn 2+ distribution can produce the distortions of the YbO 6 octahedra observed from neutron diffraction. Because the documented heterogeneity will extend to exchange interactions, our results suggest that disorder is a significant factor in the unusual magnetism previously reported in YbZn 2 ⁢GaO 5 , including broad low-energy magnetic excitations and the absence of magnetic ordering down to 0.3 K.

Crystal field excitations↗

PyCrystalField : software for calculation, analysis and fitting of crystal electric field Hamiltonians

PyCrystalField is a Python software package for calculating single-ion crystal electric field (CEF) Hamiltonians. This software can calculate a CEF Hamiltonian ab initio from a point charge model for any transition or rare earth ion in either the J basis or the LS basis, perform symmetry analysis to identify nonzero CEF parameters, calculate the energy spectrum and observables such as neutron spectrum and magnetization, and fit CEF Hamiltonians to any experimental data. Here, the theory, implementation and examples of its use are discussed.

36 MATERIALS SCIENCE↗

Optical cone beam tomography of Cherenkov-mediated signals for fast 3D dosimetry of x-ray photon beams in water

Purpose: To test the use of a three-dimensional (3D) optical cone beam computed tomography reconstruction algorithm, for estimation of the imparted 3D dose distribution from megavoltage photon beams in a water tank for quality assurance, by imaging the induced Cherenkov-excited fluorescence (CEF). Methods: An intensified charge-coupled device coupled to a standard nontelecentric camera lens was used to tomographically acquire two-dimensional (2D) projection images of CEF from a complex multileaf collimator (MLC) shaped 6 MV linear accelerator x-ray photon beam operating at a dose rate of 600 MU/min. The resulting projections were used to reconstruct the 3D CEF light distribution, a potential surrogate of imparted dose, using a Feldkamp–Davis–Kress cone beam back reconstruction algorithm. Finally, the reconstructed light distributions were compared to the expected dose values from one-dimensional diode scans, 2D film measurements, and the 3D distribution generated from the clinical Varian ECLIPSE treatment planning system using a gamma index analysis. A Monte Carlo derived correction was applied to the Cherenkov reconstructions to account for beam hardening artifacts. Results: 3D light volumes were successfully reconstructed over a 400 × 400 × 350 mm{sup 3} volume at a resolution of 1 mm. The Cherenkov reconstructions showed agreement with all comparative methods and were also able to recover both inter- and intra-MLC leaf leakage. Based upon a 3%/3 mm criterion, the experimental Cherenkov light measurements showed an 83%–99% pass fraction depending on the chosen threshold dose. Conclusions: The results from this study demonstrate the use of optical cone beam computed tomography using CEF for the profiling of the imparted dose distribution from large area megavoltage photon beams in water.

07 ISOTOPE AND RADIATION SOURCES↗

Magnetic properties of nearly stoichiometric CeAuBi{sub 2} heavy fermion compound

Motivated by the interesting magnetic anisotropy found in the heavy fermion family CeTX{sub 2} (T = transition metal and X = pnictogen), here, we study the novel parent compound CeAu{sub 1−x}Bi{sub 2−y} by combining magnetization, pressure dependent electrical resistivity, and heat-capacity measurements. The magnetic properties of our nearly stoichiometric single crystal sample of CeAu{sub 1−x}Bi{sub 2−y} (x = 0.92 and y = 1.6) revealed an antiferromagnetic ordering at T{sub N} = 12 K with an easy axis along the c-direction. The field dependent magnetization data at low temperatures reveal the existence of a spin-flop transition when the field is applied along the c-axis (H{sub c} ∼ 7.5 T and T = 5 K). The heat capacity and pressure dependent resistivity data suggest that CeAu{sub 0.92}Bi{sub 1.6} exhibits a weak heavy fermion behavior with strongly localized Ce{sup 3+} 4f electrons. Furthermore, the systematic analysis using a mean field model including anisotropic nearest-neighbors interactions and the tetragonal crystalline electric field (CEF) Hamiltonian allows us to extract a CEF scheme and two different values for the anisotropic J{sub RKKY} exchange parameters between the Ce{sup 3+} ions in this compound. Thus, we discuss a scenario, considering both the anisotropic magnetic interactions and the tetragonal CEF effects, in the CeAu{sub 1−x}Bi{sub 2−y} compounds, and we compare our results with the isostructural compound CeCuBi{sub 2}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetic order and excitations in Ce 3 TiBi 5 and Ce 3 ZrBi 5

The R 3 MBi 5 rare-earth intermetallics (R = rare earth, M = Ti, Zr, Sc) provide a versatile platform to explore how Kondo hybridization, Ruderman–Kittel–Kasuya–Yosida (RKKY) exchange, magnetic frustration, and broken inversion symmetry may cooperate to generate unusual magnetic behavior. We present a comprehensive neutron scattering investigation of the magnetic structure, crystal electric field (CEF), and low-energy excitations in the locally noncentrosymmetric Kondo-lattice compounds Ce 3 TiBi 5 and Ce 3 ZrBi 5 . Powder and single-crystal neutron diffraction reveals incommensurate cycloidal antiferromagnetic order in Ce 3 TiBi 5 with propagation vector k = (0, 0, 0.388) and a reduced ordered moment of m = 0.53(3)μ B . Ce 3 ZrBi 5 exhibits a qualitatively similar magnetic diffraction profile, with k ≃ (0, 0, 0.37). Inelastic neutron scattering measurements resolve two clear, well-separated CEF excitations in both compounds with nearly the same profile, confirming a well-isolated Kramers doublet ground state. At low energies, a broad, quasi-elastic magnetic response is observed at T ≃ T N , whose momentum-dependence is inconsistent with that expected from conventional collective excitations of localized moments. This discrepancy, along with a Kondo temperature estimate T K ~ 6 - 7 K—comparable to T N —indicates sizable Kondo hybridization, which accounts for the moment reduction and the spiral magnetic order that appears to involve the magnetic hard direction. Our results place these compounds in a regime where local inversion symmetry breaking, anisotropic CEF effects, and competing Kondo and RKKY interactions collectively give rise to unconventional magnetic order.

Kondo interaction↗

Explaining the extra crystal-field mode in 𝐴 ⁢Ce ⁢𝑋 2 (𝐴 = K, Rb, Na; 𝑋 = O, S, Se, Te)

A growing list of Ce-based magnets have shown an extra and heretofore unexplained crystal electric field (CEF) mode at high energies. We describe a process whereby an optical phonon can produce a split CEF mode well above the phonon energy. We use density functional theory and point-charge model calculations to estimate the phonon distortions and coupling to model this effect in KCeO 2 , showing that it accounts for the extra CEF mode observed. Furthermore, this mechanism is generic and may explain the extra modes observed on a variety of Ce 3+ compounds.

36 MATERIALS SCIENCE↗

Low-temperature spin dynamics in the TmFeO 3 orthoferrite with a non-Kramers ion

We investigate the magnetic dynamics of the orthorhombic perovskite TmFeO 3 at low temperatures, below the spin reorientation transition at TSR≈80 K, by means of time-of-flight neutron spectroscopy. We find that the magnetic excitation spectrum combines two emergent collective modes associated with different magnetic sublattices. The Fe subsystem orders below TN~632 K into a canted antiferromagnetic structure and exhibits sharp, high-energy magnon excitations. We describe them using linear spin-wave theory, and reveal a pronounced anisotropy between in- and out-of-plane exchange interactions, which was mainly neglected in previous reports on the spin dynamics in orthoferrites. At lower energies, we find two crystalline electrical field (CEF) excitations of Tm3+ ions at energies of ~2 and 5 meV. In contrast to the sister compound YbFeO 3 , where the Yb 3+ ions form quasi-one-dimensional chains along the c axis, the Tm excitations show dispersion along both directions in the (0KL) scattering plane. Analysis of the neutron scattering polarization factor reveals a longitudinal polarization of the 2 meV excitation. To evaluate the effect of the CEF on the Tm 3+ ions, we perform point-charge model calculations, and their results quantitatively capture the main features of Tm single-ion physics, such as energies, intensities, and polarization of the CEF transitions, and the type of magnetic anisotropy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Tuning the Kondo effect in Yb(Fe 1-x Co x ) 2 Zn 20

We study the evolution of the Kondo effect in heavy fermion compounds, Yb(Fe 1-x Co x ) 2 Zn 20 (0 ≲ x ≲ 1), by means of temperature-dependent electric resistivity and speci c heat. The ground state of YbFe 2 Zn 20 can be well described by a Kondo model with degeneracy N = 8 and a T K ~30 K. In the presence of a very similar total CEF splitting with YbFe 2 Zn 20 , the ground state of YbCo 2 Zn 20 is close to a Kondo state with degeneracy N = 2 and a much lower TK ~ 2 K. Upon Co substitution, the coherence temperature of YbFe 2 Zn 20 is suppressed, accompanied by an emerging Schottky-like feature in speci c heat associated with the thermal depopulation of CEF levels upon cooling. For 0.4 ≲ x ≲ 0.9, the ground state remains roughly the same which can be qualitatively understood by Kondo effect in the presence of CEF splitting. There is no clear indication of Kondo coherence observable in resistivity within this substitution range down to 500 mK. The coherence re-appears at around x≳ 0.9 and the coherence temperature increases with higher Co concentration levels.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Neutron scattering measurement of crystalline-electric fields in magnesium rare-earth selenide spinels

The symmetry of local moments plays a defining role in the nature of exotic ground states stabilized in frustrated magnetic materials. Here, we present inelastic neutron scattering (INS) measurements of the crystal electric field (CEF) excitations in the family of compounds Mg R 2 Se 4 ( R ϵ { Ho , Tm , Yb } ) . These compounds form in the spinel structure, with the rare-earth ions comprising a highly frustrated pyrochlore sublattice. Within the symmetry constraints of this lattice, we fit both the energies and intensities of observed transitions in the INS spectra to determine the most likely CEF Hamiltonian for each material and comment on the ground-state wavefunctions in the local electron picture. In this way, we experimentally confirm MgTm 2 Se 4 has a nonmagnetic ground state, and MgYb 2 Se 4 has effective S = 1 2 spins with g ∥ = 5.188 ( 79 ) and g ⊥ = 0.923 ( 85 ) . The spectrum of MgHo 2 Se 4 indicates a ground-state doublet containing Ising spins with g ∥ = 2.72 ( 46 ) , though low-lying CEF levels are also seen at thermally accessible energies E = 0.591 ( 36 ) , 0.945(30), and 2.88(7) meV, which can complicate interpretation. These results are used to comment on measured magnetization data of all compounds and are compared to published results on the material MgEr 2 Se 4 .

36 MATERIALS SCIENCE↗

Spin fluctuations, absence of magnetic order, and crystal electric field studies in the Yb 3+ -based triangular lattice antiferromagnet Rb 3 ⁢Yb⁢(VO 4 ) 2

Here, we report a comprehensive experimental investigation of the structural, thermodynamic, static, and dynamic properties of a triangular lattice antiferromagnet Rb 3 ⁢Yb(VO 4 ) 2 . Through the analysis of magnetic susceptibility, magnetization, and specific heat, complemented by crystal electric field (CEF) calculations, we confirm the Kramers' doublet with effective spin 𝐽 eff = 1/2 ground state. Magnetic susceptibility and isothermal magnetization analysis reveal a weak antiferromagnetic interaction among the 𝐽 eff = 1/2 spins, characterized by a small Curie-Weiss temperature (𝜃$^{\textrm{LT}}_{\textrm{CW}}$ ≃−0.26 K) or a reduced exchange coupling (𝐽/𝑘 B ≃ 0.18 K). The 51 V NMR spectra and spin-lattice relaxation rate (1/𝑇 1 ) show no evidence of magnetic long-range-order down to 1.6 K but reflect strong influence of CEF excitations in the intermediate temperatures. At low temperatures, 1/𝑇 1 ⁡(𝑇) shows pronounced frequency dependence and 1/𝑇 1 vs field at different temperatures follows the scaling behavior, highlighting the role of paramagnetic fluctuations. The CEF calculations using the point charge approximation divulge a large energy gap ( ∼18.61 meV) between the lowest and second lowest energy doublets, further establishing Kramers' doublet as the ground state. Our calculations also reproduce the experimental magnetization and specific heat data and indicate an in-plane magnetic anisotropy. These findings position Rb 3⁢ Yb(VO 4 ) 2 as an ideal candidate to explore intrinsic quantum fluctuations and possible quantum spin-liquid physics in a Yb 3+ -based triangular lattice antiferromagnet.

Sebastian, Sebin J. [Indian Institute of Science E↗

CrysFieldExplorer : rapid optimization of the crystal field Hamiltonian

A new approach to the fast optimization of crystal electric field (CEF) parameters to fit experimental data is presented. This approach is implemented in a lightweight Python-based program, CrysFieldExplorer. The main novelty of the method is the development of a unique loss function, referred to as the spectrum characteristic loss (L Spectrum ), which is based on the characteristic polynomial of the Hamiltonian matrix. Particle swarm optimization and a covariance matrix adaptation evolution strategy are used to find the minimum of the total loss function. It is demonstrated that CrysFieldExplorer can perform direct fitting of CEF parameters to any experimental data such as a neutron spectrum, susceptibility or magnetization measurements etc. CrysFieldExplorer can handle a large number of non-zero CEF parameters and reveal multiple local and global minimum solutions. Crystal field theory, the loss function, and the implementation and limitations of the program are discussed within the context of two examples.

42 ENGINEERING↗

AmeriFlux US-Cst Crossett Experimental Forest

This is the AmeriFlux version of the carbon flux data for the site US-Cst Crossett Experimental Forest. Site Description - The study takes place in the Crossett Experimental Forest (CEF, 32°2′ N, 91°57′ W), which was established in 1934 with the objective of developing effective management protocols for loblolly and shortleaf pine forests in the Gulf Coastal Plain. Mean annual temperature and precipitation are 17.6 °C and 1,410 mm, respectively. Most of the soils on and near the CEF are silt loams (primarily Glossaquic Fragiudalfs). The tower is situated in the the old-growth pine management sector of the CEF, which emphasizes management for old-growth-like conditions, with the goal of emulating the structural and compositional attributes of historic forests from this region using a combination of timber harvesting, prescribed fire, and other tools. This includes periodic commercial logging of intermediate-sized loblolly pines to support further restoration treatments, such as prescribed fire, hardwood and exotic species competition control, and the increase of plant species more compatible with fire (e.g., shortleaf pine and understory grasses)

Novick, Kim↗

AmeriFlux FLUXNET-1F US-Cst Crossett Experimental Forest

This is the AmeriFlux Management Project (AMP) created FLUXNET-1F version of the carbon flux data for the site US-Cst Crossett Experimental Forest. This is the FLUXNET version of the carbon flux data for the site US-Cst Crossett Experimental Forest produced by applying the standard ONEFlux (1F) software. Site Description - The study takes place in the Crossett Experimental Forest (CEF, 32°2′ N, 91°57′ W), which was established in 1934 with the objective of developing effective management protocols for loblolly and shortleaf pine forests in the Gulf Coastal Plain. Mean annual temperature and precipitation are 17.6 °C and 1,410 mm, respectively. Most of the soils on and near the CEF are silt loams (primarily Glossaquic Fragiudalfs). The tower is situated in the the old-growth pine management sector of the CEF, which emphasizes management for old-growth-like conditions, with the goal of emulating the structural and compositional attributes of historic forests from this region using a combination of timber harvesting, prescribed fire, and other tools. This includes periodic commercial logging of intermediate-sized loblolly pines to support further restoration treatments, such as prescribed fire, hardwood and exotic species competition control, and the increase of plant species more compatible with fire (e.g., shortleaf pine and understory grasses)

Novick, Kim↗