SEARCH · Engineering Papers
Results for “paramagnetism”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Collinear orbital antiferromagnetic order and magnetoelectricity in quasi-two-dimensional itinerant-electron paramagnets, ferromagnets, and antiferromagnets
Not Available
Giant effective magnetic fields from optically driven chiral phonons in 4 f paramagnets
Not Available
Suppressed paramagnetism in amorphous Ta 2 O 5 − x oxides and its link to superconducting-qubit performance
Amorphous-oxide layers in thin-film capacitors are linked to reduced transmon-qubit T 1 coherence times. Ta -based capacitors outperform Nb -based ones, suggesting that amorphous Ta 2 O 5 − x is less lossy than Nb 2 O 5 − x . We investigate the microscopic features of these amorphous oxides using ab initio molecular dynamics and density functional theory, revealing the origins of the superior performance of Ta 2 O 5 − x . We establish that oxygen deficiency is less likely to occur in amorphous Ta 2 O 5 − x than in Nb 2 O 5 − x for 0 ≤ x ≤ 0.25 and that for a given oxygen deficiency x , metal Ta — Ta bond formation is enhanced. Such bonds, which are accommodated by structural flaws in the amorphous network, capture electrons better than in amorphous Nb 2 O 5 − x . These thermochemical differences quench or highly suppress magnetic moments in amorphous Ta 2 O 5 − x and eliminate a potential source of quasiparticles and magnetic flux noise. We also show that hyperfine couplings between Nb nuclei and local magnetic moments in Nb 2 O 5 − x can form “two-level systems” (TLSs) or “two-level fluctuators” with energy splittings of 100–1000 MHz or higher. This reveals a TLS mechanism in amorphous Nb 2 O 5 − x oxide layers that is likely inactive in Ta 2 O 5 − x . Our work provides a fundamental understanding of the materials chemistry and limitations imposed by native oxides of superconducting qubits that can be used to guide materials selection and processing.
Electron paramagnetic resonance studies of f-element complexes
Explore the source record for details and available documents.
Investigating trends in actinide covalency and magnetism with 35/37 Cl SSNMR spectroscopy and first-principles calculations
Solid-state NMR (SSNMR) spectroscopy is a powerful technique for studying actinide chemistry but has been significantly limited due to the complex paramagnetism, and radiological hazards presented by these materials. Lanthanide and actinide salts often feature magnetic ordering and can be paramagnetic, ferromagnetic, or antiferromagnetic depending on temperature and electronic structure. Paramagnetic interactions can manifest in SSNMR both as secular spectral shifts and/or couplings as well as contributions from non-secular relaxation. Both effects can be directly measured with NMR and used to extrapolate rich chemical information such as coordination environments, bonding characteristics, local molecular dynamics, and correlation times. Typically, these studies are carried out on high-γ and highly abundant NMR-active isotopes (e.g., 1 H, 6/7 Li, 19 F, 23 Na, etc.) or on enriched rare isotopes (e.g., 2 H and 17 O), which can be expensive. Herein, we present a facile methodology to measure the 35/37 Cl electric-field gradient (EFG) and paramagnetic shift anisotropy (SA) tensor components using static wideline SSNMR measurements of LaCl 3 , NdCl 3 , UCl 3 , and UCl 4 . The static powder spectra were measured with both 35 Cl and 37 Cl SSNMR to increase the fidelity of the extracted tensor parameters. Variable temperature NMR of a select case confirms the Curie–Weiss paramagnetism. Relaxation measurements of both nuclei further corroborate observations owing to the paramagnetic relaxation enhancement and reveal simultaneous quadrupolar relaxation mechanisms. Density functional theory (DFT) calculations using Hubbard U corrections to the uranium valence orbitals show excellent agreement with experimental EFG tensor parameters and help describe the bonding characteristics in these lanthanide and actinide systems.
Monte Carlo simulation to study the effect of molecular spin state on the spatio-temporal evolution of equilibrium magnetic properties of magnetic tunnel junction based molecular spintronics devices
With a variable spin state, paramagnetic molecules can affect the impact of magnetic exchange coupling strength between two ferromagnetic electrodes. Our magnetic tunnel junction based molecular spintronics devices (MTJMSD) were successful in connecting paramagnetic single molecular magnet (SMM) between two ferromagnetic electrodes. Isolated SMM exhibited a wide range of spin states. However, it was extremely challenging to identify the SMM spin state when connected to the ferromagnetic electrodes. Our prior experimental and Monte Carlo Simulations (MCS) studies showed that paramagnetic molecules produced unprecedented strong antiferromagnetic coupling between two ferromagnets at room temperature. The overall antiferromagnetic coupling occurred when a paramagnetic SMM made antiferromagnetic coupling to the first electrode and ferromagnetic coupling to the second ferromagnetic electrode. This paper studies the impact of variable molecular spin states of the SMMs, producing strong antiferromagnetic coupling between the ferromagnetic electrodes of MTJMSD. The MTJMSD used in this study was represented by an 11 x 50 x 50 Ising model, with 11 being the thickness of the MTJMSD and 5 x 10 x 50 being each electrode’s size. We employed a continuous MCS algorithm to investigate SMM’s spin state’s impact as a function of molecular exchange coupling strength and thermal energy.
Magnetic anisotropy in uranium monosulfide probed by magnetic torque measurements
We have studied the magnetic torque in uranium monosulfide (US) single crystals to explore the magnetic anisotropy in this material. Uranium monosulfide crystallizes in a cubic, NaCl-type of crystal structure and exhibits the largest magnetocrystalline anisotropy observed in cubic systems. By performing detailed torque measurements we observe a strongly anisotropic behavior in the paramagnetic phase due to crystal defects and quadrupolar pair interactions. Our studies also confirm the presence of a large anisotropy in the ferromagnetic state of the US system with the <100>, <111>, and <110> directions being the hard, easy, and intermediate axes, respectively. Furthermore, the anisotropy in the paramagnetic phase shows similar characteristics to the anisotropy observed in the ferromagnetic phase, as characterized by second and fourth rank susceptibility terms. The similarity of the anisotropic behaviors in paramagnetic and ferromagnetic phases is the consequence of strong magnetoelastic properties in this system, which possibly lead to the rhombohedral structural distortion, not only in the ferromagnetic phase but also in the paramagnetic phase (induced by applied magnetic field).
Resolving Chemical and Spatial Heterogeneities at Complex Electrochemical Interfaces in Li-Ion Batteries
The high specific capacities of Ni-rich transition metal oxides have garnered immense interest for improving the energy density of Li-ion batteries (LIBs). Despite the potential of these materials, Ni-rich cathodes suffer from interfacial instabilities that lead to crystallographic rearrangement of the active material surface as well as the formation of a cathode electrolyte interphase (CEI) layer on the composite during electrochemical cycling. While changes in crystallographic structure can be detected with diffraction-based methods, probing the chemistry of the disordered, heterogeneous CEI layer is challenging. In this work, we use a combination of ex situ solid-state nuclear magnetic resonance (SSNMR) spectroscopy and X-ray photoemission electron microscopy (XPEEM) to provide chemical and spatial information, on the nanometer length scale, on the CEI deposited on LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) composite cathode films. XPEEM elemental maps offer insight into the lateral arrangement of the electrolyte decomposition products that comprise the CEI and paramagnetic interactions (assessed with electron paramagnetic resonance (EPR) and relaxation measurements) in 13 C SSNMR provide information on the radial arrangement of the CEI from the NMC811 particles outward. Using this approach, here we find that LiF, Li 2 CO 3 , and carboxy-containing structures are directly appended to NMC811 active particles, whereas soluble species detected during in situ 1 H and 19 F solution NMR experiments (e.g., alkyl carbonates, HF, and vinyl compounds) are randomly deposited on the composite surface. We show that the combined approach of ex situ SSNMR and XPEEM, in conjunction with in situ solution NMR, allows spatially-resolved, molecular-level characterization of paramagnetic surfaces and new insights into electrolyte oxidation mechanisms in porous electrode films.
Spectroscopic Investigation of Shallow Hole Traps in Ga- and B-doped Czochralski Silicon: Insight into Light-Induced Degradation
We report the minority carrier lifetime in B-doped Czochralski (Cz) Si declines upon carrier injection due to light-induced degradation (LID), which is attributed to the formation of a recombination-active boron-oxygen complex. Ga-doped Cz Si does not undergo LID. Previously, we showed that B-doped Cz Si undergoes a transition from paramagnetic to diamagnetic due to LID. Herein, we show that Ga-doped Cz Si remains paramagnetic upon carrier injection. This suggests that either the shallow hole traps that are formed in B-doped Cz Si are absent in Ga-doped Cz Si, or the negative-U centers in Ga-doped Cz Si do not transform into a recombination-active configuration, because the shallow acceptor trap state is shallower than the Ga acceptor level in the forbidden gap. In contrast to B-doped Cz Si, the defect signatures in Ga-doped Cz Si do not change upon light exposure, as detected by both electron paramagnetic resonance and deep-level transient spectroscopy.
Quantification of Dissolved O 2 in Bulk Aqueous Solutions and Porous Media Using NMR Relaxometry
Effects of dissolved paramagnetic oxygen (O 2 ) in water on 1 H nuclear magnetic resonance (NMR) Carr-Purcell-Meiboom-Gill (CPMG) experiments is evaluated at a 1 H Larmor frequency of 2 MHz. Dissolution of O 2 into water significantly reduces the 1 H transverse relaxation coefficient (T 2 ). For deoxygenated water, T 2 is 3388 ms, water at ambient atmospheric conditions (7.4 mg/L O2) exhibits a T2 of 2465 ms, and dissolution of 2710 mg/L O 2 further reduces T 2 to 36 ms. The results were fit with an empirical model to facilitate prediction of T 2 times for bulk water as a function of paramagnetic oxygen concentrations in solution. Dissolved O 2 also greatly influences 1 H NMR CPMG experiments of confined water in a model system composed of Berea sandstone. For this system, 90 mg/L O 2 in H 2 O enhances T 2 relaxation of bulk water such that the relaxation time is comparable to physically confined water in the sandstone pores. Given the sensitivity of NMR T 2 coefficients to paramagnetic oxygen, low-field NMR-based characterization of fluid and porous media structure requires control of dissolved oxygen, as geospatial variation in the partial pressure of O 2 alone is expected to perturb fluid and pore relaxation times by up to 60 and 36%, respectively.
Dramatic effect of electrode type on tunnel junction based molecular spintronic devices
A new class of molecular spintronic devices can be fabricated by chemically bonding magnetic molecular channels to the electrodes of a prefabricated tunnel junction with exposed side edges. Prior experimental studies showed that the cyanide-bridged octametallic molecular cluster, [(pzTp)FeIII(CN)3]4[NiII(L)]4¬[O3SCF3]4 [(pzTp) = tetra(pyrazol-1-yl)borate; L = 1-S(acetyl)tris(pyrazolyl)decane] molecule impact depended on the type of metallic electrodes used in the tunnel junction testbed. Experimental magnetization and transport studies showed a dramatic difference in molecule response on tunnel junctions with different combinations of metallic electrodes. Transport via paramagnetic molecular channels on a tunnel junction involving paramagnetic and ferromagnetic metal electrodes was dramatically different than the suppressed current state observed on tunnel junctions involving two ferromagnetic electrodes. We conducted theoretical studies to understand the experimental data and explore a wide range of electrode materials on tunnel junction-based molecular spintronics devices (TJMSD). Here, we report a Monte Carlo simulation study that focuses on understanding the effect of electrodes on the magnetic and physical properties of TJMSD. A 3D Heisenberg model of cross-junction-shaped TJMSD was used for the simulation study. We studied the effects of ferromagnetic, paramagnetic, and antiferromagnetic electrode materials. This study provides insights for designing and understanding futuristic molecular spintronics devices.
Development of (NO)Fe(N 2 S 2 ) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach
The ubiquity of sulfur–metal connections in nature inspires the design of bi- and multimetallic systems in synthetic inorganic chemistry. Common motifs for biocatalysts developed in evolutionary biology include the placement of metals in close proximity with flexible sulfur bridges as well as the presence of π-acidic/delocalizing ligands. This Account will delve into the development of a (NO)Fe(N 2 S 2 ) metallodithiolate ligand that harnesses these principles. The Fe(NO) unit is the centroid of a N 2 S 2 donor field, which as a whole is capable of serving as a redox-active, bidentate S-donor ligand. Its paramagnetism as well as the ν(NO) vibrational monitor can be exploited in the development of new classes of heterobimetallic complexes. We offer four examples in which the unpaired electron on the {Fe(NO)} 7 unit is spin-paired with adjacent paramagnets in proximal and distal positions. First, the exceptional stability of the (NO)Fe(N 2 S 2 )-Fe(NO) 2 platform, which permits its isolation and structural characterization at three distinct redox levels, is linked to the charge delocalization occurring on both the Fe(NO) and the Fe(NO) 2 supports. This accommodates the formation of a rare nonheme {Fe(NO)} 8 triplet state, with a linear configuration. A subsequent FeNi complex, featuring redox-active ligands on both metals (NO on iron and dithiolene on nickel), displayed unexpected physical properties. Our research showed good reversibility in two redox processes, allowing isolation in reduced and oxidized forms. Various spectroscopic and crystallographic analyses confirmed these states, and Mössbauer data supported the redox change at the iron site upon reduction. Oxidation of the complex produced a dimeric dication, revealing an intriguing magnetic behavior. The monomer appears as a spin-coupled diradical between {Fe(NO)} 7 and the nickel dithiolene monoradical, while dimerization couples the latter radical units via a Ni 2 S 2 rhomb. Magnetic data (SQUID) on the dimer dication found a singlet ground state with a thermally accessible triplet state that is responsible for magnetism. A theoretical model built on an H 4 chain explains this unexpected ferromagnetic low-energy triplet state arising from the antiferromagnetic coupling of a four-radical molecular conglomerate. For comparison, two (NO)Fe(N 2 S 2 ) were connected through diamagnetic group 10 cations producing diradical trimetallic complexes. Antiferromagnetic coupling is observed between {Fe(NO)} 7 units, with exchange coupling constants (J) of -3, -23, and -124 cm –1 for Ni II , Pd II , and Pt II , respectively. This trend is explained by the enhanced covalency and polarizability of sulfur-dense metallodithiolate ligands. A central paramagnetic trans-Cr(NO)(MeCN) receiver unit core results in a cissoid structural topology, influenced by the stereoactivity of the lone pair(s) on the sulfur donors. This {Cr(NO)} 5 radical bridge, unlike all previous cases, finds the coupling between the distal Fe(NO) radicals to be ferromagnetic (J = 24 cm –1 ). The stability and predictability of this S = 1/2 moiety and the steric/electronic properties of the bridging thiolate sulfurs suggest it to be a likely candidate for the development of novel molecular (magnetic) compounds and possibly materials. The role of synthetic inorganic chemistry in designing synthons that permit connections of the (NO)Fe(N 2 S 2 ) metalloligand is highlighted as well as the properties of the heterobi- and polymetallic complexes derived therefrom.
Ultra-Low Viscosity and High Magnetic Susceptibility Magnetic Ionic Liquids Featuring Functionalized Diglycolic Acid Ester Rare-Earth and Transition Metal Chelates
Magnetic ionic liquids (MILs) comprise a subcategory of ionic liquids (ILs) and contain a paramagnetic metal center allowing them to be readily manipulated by an external magnetic field. While MILs are popularly employed as solvents in catalysis, separations, and organic synthesis, most low viscosity combinations possess a hydrophilic character that limits their use in aqueous matrices. To date, no study has reported the synthesis and characterization of hydrophobic MILs with viscosities similar to those of hydrophilic MILs and organic solvents while simultaneously exhibiting enhanced magnetic and thermal properties. In this study, diglycolic acid esters are employed as ligands to chelate with paramagnetic metals to produce cations that are paired with metal chelates composed of hexafluoroacetylacetonate ligands to form MILs incorporating multiple metal centers in the cation and anion. Viscosity values below 31.6 cP were obtained for these solvents, the lowest ever reported for hydrophobic MILs. Solubilities in nonpolar solvents such as benzene were observed to be as high as 50% (w/v) MIL-to-solvent ratio while being insoluble in water at concentrations as low as 0.01% (w/v). Effective paramagnetic moment values for these solvents ranged from 5.33 to 15.56 Bohr magnetons (μB), with mixed metal MILs containing multiple lanthanides in the anion generally offering higher magnetic susceptibilities. MILs composed of ligands containing octyl substituents were found to possess thermal stabilities up to 190 °C. The synthetic strategies explored in this study exploit the highly tunable nature of the employed cation and anion pairs to design versatile ultra-low viscosity magnetoactive solvents that possess tremendous potential and applicability in liquid–liquid separation systems, catalysis, and microfluidics where the mechanical movement of the solvent can be easily facilitated using electromagnets.
Symmetry-mediated quantum coherence of W 5+ spins in an oxygen-deficient double perovskite
Elucidating the factors limiting quantum coherence in real materials is essential to the development of quantum technologies. Here we report a strategic approach to determine the effect of lattice dynamics on spin coherence lifetimes using oxygen deficient double perovskites as host materials. In addition to obtaining millisecond T 1 spin-lattice lifetimes at T ~ 10 K, measurable quantum superpositions were observed up to room temperature. We determine that T 2 enhancement in Sr 2 CaWO 6-δ over previously studied Ba 2 CaWO 6-δ is caused by a dynamically-driven increase in effective site symmetry around the dominant paramagnetic site, assigned as W 5+ via electron paramagnetic resonance spectroscopy. Further, a combination of experimental and computational techniques enabled quantification of the relative strength of spin-phonon coupling of each phonon mode. This analysis demonstrates the effect of thermodynamics and site symmetry on the spin lifetimes of W 5+ paramagnetic defects, an important step in the process of reducing decoherence to produce longer-lived qubits.
Magnetic molecules lose identity when connected to different combinations of magnetic metal electrodes in MTJ-based molecular spintronics devices (MTJMSD)
Abstract Understanding the magnetic molecules’ interaction with different combinations of metal electrodes is vital to advancing the molecular spintronics field. This paper describes experimental and theoretical understanding showing how paramagnetic single-molecule magnet (SMM) catalyzes long-range effects on metal electrodes and, in that process, loses its basic magnetic properties. For the first time, our Monte Carlo simulations, verified for consistency with regards to experimental studies, discuss the properties of the whole device and a generic paramagnetic molecule analog (GPMA) connected to the combinations of ferromagnet-ferromagnet, ferromagnet-paramagnet, and ferromagnet-antiferromagnet metal electrodes. We studied the magnetic moment vs. magnetic field of GPMA exchange coupled between two metal electrodes along the exposed side edge of cross junction-shaped magnetic tunnel junction (MTJ). We also studied GPMA-metal electrode interfaces’ magnetic moment vs. magnetic field response. We have also found that the MTJ dimension impacted the molecule response. This study suggests that SMM spin at the MTJ exposed sides offers a unique and high-yield method of connecting molecules to virtually endless magnetic and nonmagnetic electrodes and observing unprecedented phenomena in the molecular spintronics field.
Spiral spin cluster in the hyperkagome antiferromagnet Mn 3 RhSi
Local spin correlation orders emerge in a paramagnetic state, with notable examples such as the partial order, cooperative paramagnetism, and soliton spin liquid. The noncentrosymmetric intermetallic antiferromagnet Mn 3 RhSi also exhibits the local spin correlation order in the paramagnetic state as magnetic short-range order in a wide temperature range. Here, we show that the local spin correlation order has a spiral structure by neutron scattering measurement of a Mn 3 RhSi single crystal. The possible origins of the magnetic cluster formation are discussed in terms of the Lifshitz invariant and the Griffiths phase, and compared with the room-temperature skyrmion phase of Co 7 Zn 7 Mn 6 and non-Fermi liquid behavior of β-Mn.
Mott localization in the van der Waals crystal CrI 3 : A GGA+DMFT study
Using the generalized gradient approximation plus dynamical mean-field theory (GGA+DMFT) we confirm the importance of multi-orbital dynamical correlations in determining the paramagnetic insulating state of CrI 3 . Furthermore, while the ferromagnetic phase reveals weak electronic correlation effects due to strong spin-orbital polarization, the Mott insulating state of paramagnetic CrI 3 crystal is shown to be driven by the interplay between orbital-dependent one-electron lineshape and multi-orbital electronic interactions. To probe the paramagnetic Mott insulating state we performed x-ray absorption spectroscopy (XAS) measurements for the two structural phases of CrI 3 . Our study is relevant to understanding the orbital-selective electronic structure reconstruction of Mott insulators and should be applicable to other van der Waals bonded materials from bulk to the ultrathin limit.