Tricolor Ho[superscript 3 +] Photoluminescence Enhancement from Site Symmetry Breakdown in Pyrochlor
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Zhao, Yongsheng↗
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Crystal chemistry and phase equilibria of the CaO-½Ho 2 O 3 -CoO z system at 885 °C in air
Ini this work, the phase equilibrium diagram of the CaO-½Ho 2 O 3 -CoO z system was determined at 885 °C in air. This diagram offers compatibility relationships in the ternary oxide system that are essential for processing and for the understanding of properties of several thermoelectric phases in the system. Four three-phase regions and three solid solution tie-line regions were determined in the CaO-½Ho 2 O 3 -CoO z system. In the CaO-Ho 2 O 3 system, while a small solid solution region was identified for (Ho 1-x Ca x )O (3-z)/2 (0 ≤x ≤ 0.14), Ho was not present in the Ca site of CaO. Neither the reported Ho2CoO4 phase in the Ho 2 O-CoO z system nor the Ca-doped (Ho 1+x Ca1-x)CoO 4-z phase was present at 885 °C. No solid solution of the distorted perovskite, (Ho 1-x Cax)CoO 3-z , was established at this temperature. The CaO-CoO z system consists of two calcium cobaltate thermoelectric compounds. The 2D thermoelectric oxide, (Ca 3-x Ho x )Co 4 O 9-z (0 ≤x ≤ 0.5), has a misfit layered structure, and the 1D Ca 3 Co 2 O 6 consists of chains of alternating CoO 6 trigonal prisms and CoO 6 octahedra. Ca 3 Co 2 O 6 was found to be a stoichiometric compound. A comparison of the phase diagrams of the CaO -½ R 2 O 3 -CoO z (R = La, Nd, Eu, and Ho) systems is given.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Coercive Fields Exceeding 30 T in the Mixed-Valence Single-Molecule Magnet (Cp iPr5 ) 2 Ho 2 I 3
Mixed-valence dilanthanide complexes of the type (Cp iPr5 ) 2 Ln 2 I 3 (Cp iPr5 = pentaisopropylcyclopentadienyl; Ln = Gd, Tb, Dy) featuring a direct Ln–Ln σ-bonding interaction have been shown to exhibit well-isolated high-spin ground states and, in the case of the Tb and Dy variants, a strong axial magnetic anisotropy that gives rise to a large magnetic coercivity. Here, we report the synthesis and characterization of two new mixed-valence dilanthanide compounds in this series, (Cp iPr5 ) 2 Ln 2 I 3 (1-Ln; Ln = Ho, Er). Both compounds feature a Ln–Ln bonding interaction, the first such interaction in any molecular compounds of Ho or Er. Like the Tb and Dy congeners, both complexes exhibit high-spin ground states arising from strong spin–spin coupling between the lanthanide 4f electrons and a single σ-type lanthanide–lanthanide bonding electron. Beyond these similarities, however, the magnetic properties of the two compounds diverge. In particular, 1-Er does not exhibit observable magnetic blocking or slow magnetic relaxation, while 1-Ho exhibits magnetic blocking below 28 K, which is the highest temperature among Ho-based single-molecule magnets, and a spin reversal barrier of 556(4) cm –1 . Additionally, variable-field magnetization data collected for 1-Ho reveal a coercive field of greater than 32 T below 8 K, more than 6-fold higher than observed for the bulk magnets SmCo 5 and Nd 2 Fe 14 B, and the highest coercive field reported to date for any single-molecule magnet or molecule-based magnetic material. Multiconfigurational calculations, supported by far-infrared magnetospectroscopy data, reveal that the stark differences in magnetic properties of 1-Ho and 1-Er arise from differences in the local magnetic anisotropy of the lanthanide centers.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
PotLib 2023: New version of a potential energy surface library for chemical systems
POTLIB is a library of global and semiglobal potential energy surface subprograms. The library currently features 410 entries, including both single-state entries and multi-state entries. When one calls the routine of a single-state entry, it returns the ground-electronic-state adiabatic potential energy surface at the input geometry. In addition, some entries also return the gradient of the surface. Further, when one calls a multi-state entry, it returns a diabatic potential energy matrix (DPEM). If the entry also has the gradient of the DPEM, one can compute adiabatic surfaces, their gradients, and the nonadiabatic coupling vectors (NACs) from the DPEM and its gradient by diagonalization. Some but not all the routines conform to one of a set of standard interfaces. The goal is to facilitate chemical dynamics research by collecting and disseminating a comprehensive collection of state-of-the-art potential energy routines (developed by a wide, international group of researchers) with systematic and well-defined interfaces for use with chemical dynamics programs. Systems in the library include CHArO 2 , CHN 2 O + , CH 2 O, CH 2 O 2 , CH 3 N 2 , CH 3 O, CH 4 , CH 4 Br, CH 4 Cl, CH 4 F, CH 4 O, CH 4 OCl, CH 4 OF, CH 4 OH, CH 5 , CH$^{+}_{5}$, CH 5 N, CH 5 O 2 , CH 8 O 2 , C 2 H 2 N 2 O, C 2 H 2 O, C 2 H 4 N, C 2 H 4 O 4 , C 2 H 6 Cl, C 2 H 6 F, C 2 H 6 H, C 2 H 6 O, C 2 H 6 OH, C 2 H 7 , C 2 O 2 , C 3 H 4 O 2 , C 3 H 7 NO, C 6 H 6 O, C 6 H 6 S, C 7 H8S, HBrCl, HCl 2 , HF 2 , HI 2 , HLiF, HNaF, HO 2 , HO 3 , HOBr, HSiO, H 2 Br, H 2 ClO, H 2 F, H 2 F 2 , H 2 FO, H 2 Na, H 2 O, H 2 O 2 , H 2 OBr, H 3 , H 3 Cl, H 3 ClN, H 3 ClO, H 3 N, H 3 O, H 3 O 2 , H$^{+}_{3}$, H 3 S, H 4 ClSi, H 4 N, H 4 NO, H 4 O 2 , H 5 GeO, H 5 Si, H$^{+}_{7}$, Al m H n , Al n , Ar N O, K 2 Rb 2 , NO 2 , N 2 O, N 2 O 2 , N 3 , N 4 , O 3 , and O 4 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Assessment of sulfur trioxide formation due to enhanced interaction of nitrogen oxides and sulfur oxides in pressurized oxy-combustion
Pressurized oxy-combustion is emerging to be one of the best technologies for significantly decreasing the energy penalty for CO 2 capture in coal-fired power plants. However, the higher pressure boosts the formation of acid gases, including SO 3 and NO 2 , which could increase the risk of corrosion. The synergistic promotion of SO 3 and NO 2 formation in pressurized oxy-combustion is kinetically evaluated under representative conditions (1 ~ 30 atm, 600 ~ 1200 °C, NO/SO 2 = 0.1 ~ 5). We begin with a comprehensive mechanism (72 species and 428 reactions), covering nitrogen and sulfur chemistry, relying on GRI-Mech 3.0. This analysis shows that the interaction of SO X and NO X enhances the conversion rates of SO 2 → SO 3 , and this effect is more apparent at elevated pressures and lower temperatures. Mechanism analyses indicate that at elevated pressures, the formation pathways of SO 3 through HOSO 2 + O 2 = SO 3 + HO 2 , and NO 2 through HO 2 + NO = NO 2 + OH, are promoted due to the strong interaction between SO X and NO X . The intermediate between these two reactions is SO 2 + OH + M = HOSO 2 + M, resulting in a strong cycle, that can be expressed by the global reaction NO + SO 2 + O 2 = NO 2 + SO 3 . Finally, a nine-step reduced chemistry is developed and validated to accurately predict the formation of SO 3 in the post-flame region at elevated pressures.
42 ENGINEERING↗
Spin-orbital order and excitons in magnetoresistive HoBi
The magnetism of the rocksalt fcc rare-earth monopnictide HoBi, a candidate topological material with extreme magnetoresistance, is investigated. From the Ho 3+ non-Kramers J=8 spin-orbital multiplet, the cubic crystal electric field yields six nearly degenerate low-energy levels. These constitute an anisotropic magnetic moment with a Jahn-Teller-like coupling to the lattice. In the cubic phase for T>T N =5.72(1)K, the paramagnetic neutron scattering is centered at k=($\frac{1}{2}$$\frac{1}{2}$$\frac{1}{2}$) and was fit to dominant antiferromagnetic interactions between Ho spins separated by {100} and ferromagnetic interactions between spins displaced by {$\frac{1}{2}$ $\frac{1}{2}$ 0}. For T < T N , a type-II AFM long-range order with k=($\frac{1}{2}$$\frac{1}{2}$$\frac{1}{2}$) develops along with a tetragonal lattice distortion. While neutron diffraction from a multidomain sample cannot unambiguously determine the spin orientation within a domain, the bulk magnetization, structural distortion, and our measurements of the magnetic excitations all show the easy axis coincides with the tetragonal axis. Finally, the weakly dispersive excitons for T < T N can be accounted for by a spin Hamiltonian that includes the crystal electric field and exchange interactions within the random phase approximation.
36 MATERIALS SCIENCE↗
Local site behavior of the 5$d$ and 4$f$ ions in the frustrated pyrochlore Ho 2 Os 2 O 7
The pyrochlore osmate Ho 2 Os 2 O 7 is a candidate material for a fragile J=0 local singlet ground state, however little is known regarding the single-ion behavior of either the Os or Ho ions. To address this we present polarized neutron powder diffraction (PNPD) and resonant inelastic x-ray scattering (RIXS) measurements that separately probe the local site behavior of the Os and Ho ions. The PNPD results are dominated by Ho 3+ scattering and the analysis reveals local site susceptibility behavior consistent with spin ice materials. Complimentary unpolarized neutron powder diffraction show an ordered spin ice ground state in an applied magnetic field. To isolate the Os 4+ single-ion behavior we present resonant inelastic x-ray scattering (RIXS) measurements at the osmium L-edge. Analysis of the RIXS spectra parameterize the spin-orbit coupling (0.35 eV), Hund’s coupling (0.27 eV) and trigonal distortion (-0.17 eV). Here, the results are considered within the context of a J=0 model and possible departures from this through structural distortions, excitonic interactions and 5d-4f interactions between the Os ion and the surrounding Ho lattice. The experimental methodology employed highlights the complimentary information available in rare earth based 5d pyrochlores from distinct neutron and x-ray scattering techniques that allow for the isolation and determination of the behavior of the different ions.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Chloride Insertion Enhances the Electrochemical Oxidation of Iron Hydroxide Double-Layer Hydroxide into Oxyhydroxide in Alkaline Iron Batteries
Rechargeable alkaline iron batteries that constitute environmentally benign electrolytes and earth-abundant industrial materials are desirable green solutions for large-scale energy storage. As one of the most abundant metal elements in the earth’s crust, iron (Fe) can satisfy nearly all criteria for low-cost and safe battery electrodes. However, challenges in achieving reversible Fe redox impede their extensive implementation in modern energy supply systems. Here, this study revealed that Cl-anion insertion into Fe(OH) 2 layered double hydroxide (LDH) formed a green rust intermediate phase with the formula [Fe 2 2+ Fe 1 3+ (HO – ) 6 ] + [Cl] – , which assisted a high Fe(OH) 2 /FeOOH conversion reaction (64.7%) and improved cycling stability. This new iron redox chemistry was validated by operando X-ray diffraction, electrochemical testing, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS) analysis, scanning transmission electron microscopy–energy-dispersive X-ray spectroscopy (STEM-EDS) mapping, and molecular dynamics (MD) simulations. Our study provides new insight into designing LDH materials for high-capacity alkaline iron batteries.
36 MATERIALS SCIENCE↗
High-order harmonics and the reverse of the squaring up process in the triangular-lattice magnet HoPdAl 4 Ge 2
We uncover high-order harmonics and the reverse of the squaring-up process, in terms of analyzing the evolution of magnetic orders in a centrosymmetric layered triangular-lattice magnet HoPdAl 4 Ge 2 , based on a detailed study of the crystal structure, magnetic susceptibility, magnetization, heat capacity, and magnetic structure. Temperature dependencies of magnetic susceptibility and heat capacity show two magnetic transitions at T N = 10.5 K and T t = 5.5 K. Below T N , Ho 3+ spins order antiferromagnetically as a transverse spin-density wave with the propagation vector k 1 = (001.5 – δ) with δ ≈ 0.18. Upon further cooling through T t , the high-order harmonics with k n = (001.5 – nδ), n = 3, 5, 7 develop, suggesting a squaring-up process. It is surprising that the squaring-up process does not continue down to 0 K but reverses the trend below 3 K. Magnetic-field-induced metastable transitions were observed in M(H) curves with the fields applied both parallel and perpendicular to the triangular-lattice plane. Neutron-diffraction results suggest that the magnetization process in HoPdAl 4 Ge 2 involves the conversion of k n = (001.5 – nδ) with n = 1, 3, 5, 7, to a ferromagnetic k F = (000) component. It is worth noting that the already weak seventh harmonic magnetic peak is enhanced by applying a small magnetic field in the ab plane at 1.5 K or warming up to 3 K, accompanied by a slight decrease of δ.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Intermolecular Coulombic Decay in Endohedral Fullerene at the 4 d → 4 f Resonance
Intermolecular processes offer unique decay mechanisms for complex systems to internally relax. Here, we report the observation of an intermolecular Coulombic decay channel in an endohedral fullerene, a holmium nitride complex (Ho 3 N) embedded within a C 80 fullerene, between neighboring holmium ions, and between the holmium complex and the carbon cage. By measuring the ions and the electrons in coincidence after XUV photoabsorption, we can isolate the different decay channels, which are found to be more prevalent relative to intra-atomic Auger decay.
74 ATOMIC AND MOLECULAR PHYSICS↗
Vibronic Relaxation Pathways in Molecular Spin Qubit Na 9 [Ho(W 5 O 18 ) 2 ]·35H 2 O under Pressure
In order to explore how spectral sparsity and vibronic decoherence pathways can be controlled in a model qubit system with atomic clock transitions, we combined diamond anvil cell techniques with synchrotron-based far infrared spectroscopy and first-principles calculations to reveal the vibrational response of Na 9 [Ho(W 5 O 18 ) 2 ]·35H 2 O under compression. Because the hole in the phonon density of states acts to reduce the overlap between the phonons and f manifold excitations in this system, we postulated that pressure might move the HoO 4 rocking, bending, and asymmetric stretching modes that couple with the M J = ±5, ±2, and ±7 levels out of resonance, reducing their interactions and minimizing decoherence processes, while a potentially beneficial strategy for some molecular qubits, pressure slightly hardens the phonons in Na 9 [Ho(W 5 O 18 ) 2 ]·35H 2 O and systematically fills in the transparency window in the phonon response. The net result is that the vibrational spectrum becomes less sparse and the overlap with the various M J levels of the Ho 3+ ion actually increases. These findings suggest that negative pressure, achieved using chemical means or elongational strain, could further open the transparency window in this rare earth-containing spin qubit system, thus paving the way for the use of device surfaces and interface elongational/compressive strains to better manage decoherence pathways.
36 MATERIALS SCIENCE↗
Ho:Tm:Lu(3)Al(5)O(12) As An Infrared-Laser Material
Material selected on basis of quantum-mechanical modeling of lasing properties. Ho:Tm:Lu(3)Al(5)O(12) features relatively low thermal occupation of lower laser level because this level higher than corresponding levels of most other available laser materials. In addition, it has reasonably large effective cross section for stimulated emission because of contribution of several transitions around central strong transition. Yet another desirable property is its calculated rate of upconversion is lower than those of other laser materials. Inasmuch as upconversion detracts from efficiency of laser, this lower rate of upconversion is highly desirable.
Barnes, Norman P.↗
Oxidation of methylamine
A detailed chemical kinetic model for oxidation of methylamine has been developed, based on theoretical work and a critical evaluation of data from the literature. In this work, the rate coefficients for the reactions of CH 3 NH 2 + O 2 → CH 2 NH 2 / CH 3 NH + HO 2 , CH 3 NH 2 + H → CH 3 + NH 3 , CH 3 NH → CH 2 NH 2 , and CH 3 NH + O 2 → CH 2 NH + HO 2 were calculated from ab initio theory. The mechanism was validated against experimental results from batch reactors, flow reactors, shock tubes, and premixed flames. The model predicts satisfactorily explosion limits for CH 3 NH 2 and its oxidation in a flow reactor. However, oxidation in the presence of nitric oxide, which strongly promotes reaction at lower temperatures, is only described qualitatively. Furthermore, calculated flame speeds are higher than reported experimental values; the model does not capture the inhibiting effect of the NH 2 group in CH 3 NH 2 compared to CH 4 . More work is desirable to confirm the products of the CH 3 NH + NO reaction and to look into possible pathways to NH 3 in methylamine oxidation.
10 SYNTHETIC FUELS↗
Resistivity and magnetoresistance properties of R 2 NiSi 3 (R = Gd, Dy, Ho, Er, Tm) compounds
The resistivity and magnetoresistance behaviour of the hexagonal intermetallic compounds R 2 NiSi 3 (R = Gd, Dy, Ho, Er, and Tm) are reported here. All the studied polycrystalline compounds exhibit metallic behavior along with additional magnetic anomalies at low temperatures. A well-defined resistivity minima is observed in Gd 2 NiSi 3 and Dy 2 Ni 0.87 Si 2.95 at a temperature much higher than their respective magnetic transition temperatures. The anomaly has been ascribed to the charge carrier localization caused by magnetic precursor effect. Magnetic field induced crossover from positive to negative magnetoresistance (MR) behavior associated with antiferromagnetic ground state is evidenced for Gd 2 NiSi 3 and Er 2 NiSi 3 in the low temperature region. Although Tm 2 Ni 0.93 Si 2.93 does not exhibit any long range magnetic order down to 2 K, a sudden drop in resistivity behavior is observed below ~10 K. Furthermore, presence of short range magnetic correlation observed in a wide temperature range, much beyond their respective magnetic ordering temperatures, has been argued to be responsible for achieving finite negative MR for all the compounds. Additionally, a subtle resemblance between the observed transport anomalies and the magnetic properties of these systems has been discussed.
36 MATERIALS SCIENCE↗
Magnetocapacitance effect and magnetoelectric coupling in type-II multiferroic HoFeWO 6
We have investigated the multiferroicity and magnetoelectric (ME) coupling in HoFeWO 6 . With a noncentrosymmetric polar structure (space group Pna2 1 ) at room temperature, this compound shows an onset of electric polarization with an antiferromagnetic ordering at the Néel temperature (T N ) of 17.8 K. The magnetic properties of the polycrystalline samples were studied by DC and AC magnetization and heat capacity measurements. The metamagnetic behavior at low temperatures was found to be directly related to the dielectric properties of the compound. In particular, field-dependent measurements of capacitance show a magnetocapacitance (MC) effect with double-hysteresis loop behavior in direct correspondence with the magnetization. Our x-ray diffraction results show the Pna2 1 structure down to 8 K and suggest the absence of a structural phase transition across T N . Soft x-ray absorption spectroscopy and soft x-ray magnetic circular dichroism (XMCD) measurements at the Fe L 2,3 and Ho M 4,5 edges revealed the oxidation state of Fe and Ho cations to be 3+. Fe L 2,3 XMCD further shows that Fe 3+ cations are antiferromagnetically ordered in a noncollinear fashion with spins arranged 90° with respect to each other. Our findings show that HoFeWO 6 is a type-II multiferroic exhibiting a MC effect. Furthermore, the observed MC effect and the change in polarization by the magnetic field, as well as their direct correspondence with magnetization, further support the strong ME coupling in this compound.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Space shuttle: Aerodynamic characteristics of various MDAC space shuttle ascent configurations with parallel burn pressure-fed and SRM boosters. Volume 1: Tanks T1 and T2 ascent configurations
Various space shuttle ascent configurations were tested in a trisonic wind tunnel to determine the aerodynamic characteristics. The ascent configuration consisted of a NASA/MSC 040 orbiter in combination with various HO centerline tank and booster geometries. The aerodynamic interference between components of the space shuttle and the effect on the orbiter aerodynamics was determined. The various aerodynamic configurations tested were: (1) centerline HO tanks T1 and T2, (2) centerline HO tank T3, and (3) centerline HO tank H4.
Jarrett, T. W.↗
Systematic study of short- and long-range correlations in RE 3 TaO 7 weberite-type compounds by neutron total scattering and X-ray diffraction
The atomic structures of the lanthanide tantalates, Ln 3 TaO 7 , series (Ln = Pr, Tb, Dy, Ho, Tm, Yb) were systematically investigated using total scattering techniques. High-energy X-ray and neutron diffraction analysis revealed that the long-range structures can be grouped into three distinct families: (1) ordered Cmcm (Ln = Pr), (2) ordered Ccmm (Ln = Tb, Dy, Ho), and (3) disordered, defect-fluorite Fm$\bar{3}$m (Ln = Ho, Tm, Yb). These findings help to clarify the symmetry discrepancy for the already reported long-range structures in the literature. The short-range analysis of neutron total scattering data via pair distribution functions reveals a high degree of structural heterogeneity across length scales for all compounds, with distinct local atomic arrangements that are not fully captured by the average, long-range structure. The short-range structures at the level of coordination polyhedra are better captured by a set of alternative non-centrosymmetric structural models: (1) C2cm, (2) C222 1 , and (3) C2mm. This establishes a short-range multiferroic character for weberite-type tantalates because ferroelectric interactions compete with magnetic correlations. These ferroelectric interactions are particularly pronounced for the disordered compounds Tm 3 TaO 7 and Yb 3 TaO 7 . In conclusion, the structural differences among the three families are the result of changes in TaO 6 polyhedral tilt (transition between families 1 and 2) and dipolar interactions of off-centered Ta cations (transition between families 2 and 3).
36 MATERIALS SCIENCE↗
Gen 3 Particle Pilot Plant (G3P3) -- High-Temperature Particle System for Concentrating Solar Power (Phases 1 and 2)
The U.S. Department of Energy Solar Energy Technologies Office initiated the Generation 3 Concentrating Solar Power (CSP) program to achieve higher operating temperatures (>700 °C) to enable next-generation CSP high-temperature power cycles such as the supercritical CO 2 (sCO2) Brayton Cycle. Three teams were selected to pursue high-temperature gas, liquid, and solid pathways for the heat-transfer media. Phases 1 and 2, which lasted from 2018 – 2020, consisted of design, modeling, and testing activities to further de-risk each of the technologies and develop a design for construction, commissioning, and operation of a pilot-scale facility in Phase 3 (2021 – 2024). This report summarizes the activities in Phases 1 and 2 for the solid-particle pathway led by Sandia National Laboratories. In Phases 1 and 2, Sandia successfully de-risked key elements of the proposed Gen 3 Particle Pilot Plant (G3P3) by improving the design, operation, and performance of key particle component technologies including the receiver, storage bins, particle-to-sCO2 heat exchanger, particle lift, and data acquisition and controls. Modeling and testing of critical components have led to optimized designs that meet desired performance metrics. Detailed drawings, piping and instrumentation diagrams, and process flow diagrams were generated for the integrated system, and structural analyses of the assembled tower structure were performed to demonstrate compliance with relevant codes and standards. Instrumentation and control systems of key subsystems were also demonstrated. Together with Bridgers & Paxton, Bohannan Huston, and Sandia Facilities, we have completed a 100% G3P3 tower design package with stamped engineering drawings suitable for construction bid in Phase 3.
14 SOLAR ENERGY↗