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At least 1,135 records · Page 63
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Tunable Magnetic Exchange between Rare-Earth Metal 5d and Iron 3d States: A Case Study of the Multiple Magnetic Transitions in Gd 6 FeBi 2 and the Solid Solutions Dy 6– x Gd x FeBi 2 (1 ≤ x ≤ 5) with Curie Temperatures in the Range 120–350 K

In this paper, the room-temperature magnet Gd 6 FeBi 2 was comprehensively characterized by means of temperature-dependent single-crystal X-ray diffraction, magnetization measurements, and experimental electron density and electronic structure computations. This work explores the electron-spin effects of Fe on this structure and suggests that Gd6FeBi2 shows structural features and exchange interactions, which are clearly distinguishable from other analogues, including the solid solutions Dy 6–x Gd x FeBi 2 (0 ≤ x ≤ 5). The unique traits of Gd 6 FeBi 2 and its derivatives encompass abnormal variations of lattice parameters with the temperature, as well as the presence of multiple magnetic transitions of complex nature. Based on the comprehensive analyses, it can be suggested that the unique magnetic response in this material is the result from tunable Fe spin states, which are coupled with strong Gd 5d–Fe 3d interactions, which differ from other members of this large, structural family. In the ground state, according to density functional theory calculations, the Fe atom carries two net electrons, whose spins are coupled in an antiparallel fashion to the spins of the Gd electrons. Near the Curie temperature, the Fe net moment is reduced intermittently, coupled with a multiple of magnetic transitions. The magnetic correlations are manifested in unexpected variations of the lattice parameters as a function of temperature, suggesting spin–lattice interactions. Furthermore, this study emphasizes the important role of Gd 5d electrons in tuning Fe 3d-based magnetic contribution, which enables better understanding on the spin coupling in other related compounds and sheds light on the development of new magnetic and spintronic compounds.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Exchange-biased quantum tunnelling of magnetization in a [Mn 3 ] 2 dimer of single-molecule magnets with rare ferromagnetic inter-Mn 3 coupling

A covalently-linked dimer of two single-molecule magnets (SMMs), [Mn 6 O(O 2 CMe) 6 (1,3-ppmd) 3 ](ClO 4 ) 2 , has been synthesized from the reaction of [Mn 3 O(O 2 CMe) 6 (py) 3 ](ClO 4 ) with 1,3-phenylene-bis(pyridin-2-ylmethanone) dioxime (1,3-ppmdH 2 ). It contains two [Mn III 3 O] +7 triangular units linked by three 1,3-ppmd 2 - groups into an [Mn 3 ] 2 dimer with D 3 symmetry. Solid-state dc and ac magnetic susceptibility measurements showed that each Mn 3 subunit retains its properties as an SMM with an S = 6 ground state. Magnetization vs. dc field sweeps on a single crystal reveal hysteresis loops below 1.3 K exhibiting exchange-biased quantum tunnelling of magnetization (QTM) steps with a bias field of +0.06 T. This is the first example of a dimer of SMMs showing a positive exchange bias of the QTM steps in the hysteresis loops, and it has therefore been subjected to a detailed analysis. Simulation of the loops determines that each Mn3 unit is exchange-coupled with its neighbour primarily through the 1,3-ppmd 2 - linkers, confirming a weak ferromagnetic inter-Mn 3 interaction of J 12 ≈ +6.5 mK ($\hat{H}= -2J\hat{S}_i·\hat{S}_j$ convention). High-frequency EPR studies of a microcrystalline powder sample enable accurate determination of the zero-field splitting parameters of the uncoupled Mn3 SMMs, while also confirming the weak exchange interaction between the two SMMs within each [Mn 3 ] 2 dimer. The combined results emphasize the ability of designed covalent linkers to generate inter-SMM coupling of a particular sign and relative magnitude, and thus the ability of such linkers to modulate the quantum physics. As such, this article supports the feasibility of using designed covalent linkers to develop molecular oligomers of SMMs, or other magnetic molecules, as multi-qubit systems and/or other components of new quantum technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Hydrogen bonds and dispersion forces serving as molecular locks for tailored Group 11 bis(amidine) complexes

A flexible polydentate bis(amidine) ligand LH 2 , LH 2 = {CH 2 NH( t Bu)C=N-2-(6-MePy)} 2 , operates as a molecular lock for various coinage metal fragments and forms the dinuclear complexes [LH 2 (MCl) 2 ], M = Cu (1), Au (2), the coordination polymer [{(LH 2 ) 2 (py) 2 (AgCl) 3 }(py) 3 ] n (3), and the dimesityl-digold complex [LH 2 (AuMes) 2 ] (4) by formal insertion of MR fragments (M = Cu, Ag, Au; R = Cl, Mes) into the N–H∙∙∙N hydrogen bonds of LH 2 in yields of 43–95%. Complexes 1, 2, and 4 adopt C 2 -symmetrical structures in the solid state featuring two interconnected 11-membered rings that are locked by two intramolecular N–H∙∙∙R–M hydrogen bonds. QTAIM analyses of the computational geometry-optimized structures 1a, 2a, and 4a reveal 13, 11, and 22 additional bond critical points, respectively, all of which are related to weak intramolecular attractive interactions, predominantly representing dispersion forces, contributing to the conformational stabilization of the C2-symmetrical stereoisomers in the solid state. Variable-temperature 1 H NMR spectroscopy in combination with DFT calculations indicate a dynamic conformational interconversion between two C 2 -symmetrical ground state structures in solution (ΔG ‡ c = 11.1–13.8 kcal mol –1 ), which is accompanied by the formation of an intermediate possessing C i symmetry that retains the hydrogen bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A self-consistent field formulation of excited state mean field theory

In this work, we show that, as in Hartree-Fock theory, the orbitals for excited state mean field theory can be optimized via a self-consistent one-electron equation in which electron-electron repulsion is accounted for through mean field operators. In addition to showing that this excited state ansatz is sufficiently close to a mean field product state to admit a one-electron formulation, this approach brings the orbital optimization speed to within roughly a factor of two of ground state mean field theory. The approach parallels Hartree Fock theory in multiple ways, including the presence of a commutator condition, a one-electron mean-field working equation, and acceleration via direct inversion in the iterative subspace. When combined with a configuration interaction singles Davidson solver for the excitation coefficients, the self-consistent field formulation dramatically reduces the cost of the theory compared to previous approaches based on quasi-Newton descent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Interfacial charge transfer and its impact on transport properties of LaNiO 3 /LaFeO 3 superlattices

Charge transfer or redistribution at oxide heterointerfaces is a critical phenomenon, often leading to remarkable properties such as two-dimensional electron gas and interfacial ferromagnetism. Despite studies on LaNiO 3 /LaFeO 3 superlattices and heterostructures, the direction and magnitude of the charge transfer remain debated, with some suggesting no charge transfer due to the high stability of Fe 3+ (3d 5 ). Here, we synthesized a series of epitaxial LaNiO 3 /LaFeO 3 superlattices and demonstrated partial (up to ~0.5 e - /interface unit cell) charge transfer from Fe to Ni near the interface, supported by density functional theory simulations and spectroscopic evidence of changes in Ni and Fe oxidation states. The electron transfer from LaFeO 3 to LaNiO 3 and the subsequent rearrangement of the Fe 3d band create an unexpected metallic ground state within the LaFeO 3 layer, strongly influencing the in-plane transport properties across the superlattice. Moreover, we establish a direct correlation between interfacial charge transfer and in-plane electrical transport properties, providing insights for designing functional oxide heterostructures with emerging properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Algebraic Bethe Circuits

The Algebraic Bethe Ansatz (ABA) is a highly successful analytical method used to exactly solve several physical models in both statistical mechanics and condensed-matter physics. Here we bring the ABA into unitary form, for its direct implementation on a quantum computer. This is achieved by distilling the non-unitary R matrices that make up the ABA into unitaries using the QR decomposition. Our algorithm is deterministic and works for both real and complex roots of the Bethe equations. We illustrate our method on the spin-$\frac{1}{2}$ XX and XXZ models. We show that using this approach one can efficiently prepare eigenstates of the XX model on a quantum computer with quantum resources that match previous state-of-the-art approaches. We run small-scale error mitigated implementations on the IBM quantum computers, including the preparation of the ground state for the XX and XXZ models on 4 sites. Finally, we derive a new form of the Yang-Baxter equation using unitary matrices, and also verify it on a quantum computer.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2026

Electron-doping-induced destabilization of the dimerized insulating state in monolayer IrTe 2

The ability to tune the electronic phases of two-dimensional (2D) materials through external perturbations provides a powerful route to engineer functional nanoscale systems. In particular, the ground state of monolayer (ML) 1T-IrTe 2 is highly sensitive to the interplay between local chemical bonding and global electronic topology, leading to a unique 2 × 1 dimerized insulating phase. Here, we present an angle-resolved photoemission study on the evolution of the electronic structure in ML IrTe 2 induced by in situ Rb adsorption. We find that Rb adsorption suppresses the 2 × 1 dimerized phase in ML IrTe 2 , inducing a clear insulator-to-metal transition. This transition is characterized by a reconstruction of the band topology toward a bilayer-like metallic configuration. Combined with first-principles calculations, our results demonstrate that the collapse of the insulating state originates from Ir valence change and suppression of Fermi surface nesting-driven instabilities. Our findings establish ML IrTe 2 as a model system for investigating instability-driven phase control in 2D materials and highlight its potential for tunable electronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Phonon dynamics in quantum spin liquid and valence bond crystal states in the barlowite family of kagome magnets

The barlowite [Cu 4 ⁢(OD) 6⁢ FBr] family of materials is characterized by antiferromagnetic spin-1/2 kagome layers and are believed to host interesting ground states of quantum magnetism. Substituting the interlayer sites with zinc ions yields Zn-barlowite (Zn 𝑥 ⁢Cu 4−𝑥 ⁢(OD) 6 ⁢FBr, 𝑥 ≈ 0.80) which is a strong candidate to have a quantum spin liquid (QSL) state. Experimentally distinguishing between valence bond crystal (VBC) and QSL states in the absence of magnetic ordering can prove challenging as both states exhibit similar average spin-spin correlations. Using high-resolution inelastic x-ray scattering with 1.4 meV energy resolution, we probe acoustic phonons in these structurally similar materials at various temperatures. Our measurements uncover robust differences possibly driven by different spin-phonon physics in VBC and QSL states, particularly at the 𝑀-point Brillouin zone boundary. Over a large 𝑇=[15,200]⁢ K temperature range, where neither material undergoes magnetic ordering nor a structural transition, we observe phonon softening in Zn-barlowite in contrast to a hardening of the same phonon in barlowite. Further, these results indicate that acoustic phonons in the barlowite system can be used to study and possibly distinguish between QSL and disordered VBC states in quantum magnets.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Nuclear Data Sheets for A=48

Experimental nuclear structure data from various reactions and decays are compiled and evaluated for all known nuclides with mass number A=48 (S, Cl, Ar, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni). For each nuclide, detailed evaluated nuclear structure information is presented for each individual reaction and decay, and the best values combining all available data are recommended for spectroscopic properties, such as level energies, half-lives, γ-ray energies and intensities, decay radiations. No excited states have been identified in 48 S, 48 Cl, 48 Co and 48 Ni, among which the first three even have no measured ground-state half-lives and decay modes. For 48 Fe, a level scheme with a sequence of excited states was established for the first time from a recent one-neutron removal measurement by 2021Ya33. Data for excited states in 48 Ar, 48 K and 48 Mn remain limited; no decay scheme has been measured for 48 Ar and 48 K yet, while the decay scheme for 48 Ni is incomplete due to unobserved levels. 48 Ti is the most studied nuclide through various reactions and decays, followed by 48 V, 40 Ca, 48 Sc, and 48 Cr, among which no decay event to 48 Sc has been observed and the decay schemes for 48 V and 48 Cr are considered as incomplete. Furthermore, this work supersedes the previous full evaluations of A=48: 2006Bu08, 1993Bu04, 1985Al14, 1978Be01.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Biased Spin-State Energetics of Fe(II) Molecular Complexes within Density-Functional Theory and the Linear-Response Hubbard U Correction

The spin-state energetics of six Fe(II) molecular complexes are computed using the linear-response Hubbard U approach within DFT. The adiabatic energy differences, ΔE H-L , between the high-spin (S = 2) and the low-spin (S = 0) states are computed and compared with accurate-coupled cluster-corrected CASPT2 results. We show that DFT+U fails in correctly capturing the ground state for strong-field ligands yielding ΔE H-L that are almost constant throughout the molecular series. This bias toward high spin together with the metal/ligand charge transfer upon U correction are here quantified and explained using molecular orbital diagrams involving both σ- and π-bonding interactions. Furthermore, with increasing ligand-field strengths this bias also increases owing to the stronger molecular character of the metal/ligand Kohn–Sham orbitals thus resulting in large deviations from the reference larger than 4 eV. Smaller values of U can be employed to mitigate this effect and recover the right energetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

I ntera C hem : Exploring Excited States in Virtual Reality with Ab Initio Interactive Molecular Dynamics

InteraChem is an ab initio interactive molecular dynamics (AI-IMD) visualizer that leverages recent advances in virtual reality hardware and software, as well as the graphical processing unit (GPU)-accelerated TeraChem electronic structure package, in order to render quantum chemistry in real time. We introduce the exploration of electronically excited states via AI-IMD using the floating occupation molecular orbital-complete active space configuration interaction method. The optimization tools in InteraChem enable identification of excited state minima as well as minimum energy conical intersections for further characterization of excited state chemistry in small- to medium-sized systems. We demonstrate that finite-temperature Hartree–Fock theory is an efficient method to perform ground state AI-IMD. InteraChem allows users to track electronic properties such as molecular orbitals and bond order in real time, resulting in an interactive visualization tool that aids in the interpretation of excited state chemistry data and makes quantum chemistry more accessible for both research and educational purposes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Balancing Panchromatic Absorption and Multistep Charge Separation in a Compact Molecular Architecture

A panchromatic triad and a charge-separation triad are joined in a crossbar architecture to capture solar energy. The panchromatic triad (T) is comprised of a central free-base porphyrin that is strongly coupled via direct ethyne linkages to two perylene-monoimides. Here, the charge-separation unit incorporates a free-base or zinc chlorin (C or ZnC) as a hole acceptor (or electron donor) and a perylene-diimide (PDI) as an electron acceptor, both attached to the porphyrin via diphenylethyne linkers. The free-base porphyrin is common to both light-harvesting and charge-separation motifs. The chlorin and PDI also function as ancillary light absorbers, complementing direct excitation of the panchromatic triad to produce the discrete lowest excited state of the array (T*). Attainment of full charge separation across the pentad entails two steps: (1) an initial excited-state hole/electron transfer process to oxidize the chlorin (and reduce the triad) or reduce the PDI (and oxidize the triad); and (2) subsequent ground-state electron/hole migration to produce oxidized chlorin and reduced PDI. Full charge separation for pentad ZnC-T-PDI to generate ZnC + -T-PDI¯ occurs with a quantum yield of ~30% and mean lifetime ~1 μs in dimethyl sulfoxide. For C-T-PDI, initial charge separation is followed by rapid charge recombination. The molecular designs and studies reported here reveal the challenges of balancing the demands for charge separation (linker length and composition, excited-state energies, redox potentials, and medium polarity) with the constraints for panchromatic absorption (strong electronic coupling of the porphyrin and two perylene-monoimide units) for integrated function in solar-energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Kinetics vs Thermodynamics: Engineering Photoredox Reactivity from an Upper Excited State of Fe II

Ultrafast deactivation of metal-to-ligand charge-transfer (MLCT) states into low-lying metal-centered states has long limited the utility of first-row transition-metal complexes in a broad range of applications, including photoredox catalysis. Here we bypass such limitations using a Fe II -pyridinium carbene complex to enable electron transfer reactivity directly from a higher-lying MLCT state. Time-resolved spectroscopic data revealed that the higher-energy MLCT manifold relaxes to lower-lying metal-centered states with a time constant of ca. 3 ps. The nature of the metal-centered (MC) excited state as a 3 MC (i.e., S = 1) was inferred from variable-temperature transient absorption studies. These experiments also revealed that the ground-state recovery process occurs at or very near the “Marcus barrierless regime”, thereby allowing for an estimate of its excited-state redox potential. The detailed picture of the energetics of this compound that emerged enabled fine-tuning of competing thermodynamic and kinetic pathways to effect electron transfer from the higher-energy MLCT excited state prior to relaxation to the ligand-field manifold. We believe these results open an unexplored landscape for the use of earth-abundant first-row transition-metal-based chromophores for applications in light-to-chemical energy conversion.

charge transfer↗
DOE OSTI2024

Imaging moiré excited states with photocurrent tunnelling microscopy

Moiré superlattices provide a highly tuneable and versatile platform to explore novel quantum phases and exotic excited states ranging from correlated insulators to moiré excitons. Scanning tunnelling microscopy has played a key role in probing microscopic behaviours of the moiré correlated ground states at the atomic scale. However, imaging of quantum excited states in moiré heterostructures remains an outstanding challenge. In this report we develop a photocurrent tunnelling microscopy technique that combines laser excitation and scanning tunnelling spectroscopy to directly visualize the electron and hole distribution within the photoexcited moiré exciton in twisted bilayer WS 2 . The tunnelling photocurrent alternates between positive and negative polarities at different locations within a single moiré unit cell. This alternating photocurrent originates from the in-plane charge transfer moiré exciton in twisted bilayer WS 2 , predicted by our GW-Bethe–Salpeter equation calculations, that emerges from the competition between the electron–hole Coulomb interaction and the moiré potential landscape. Our technique enables the exploration of photoexcited non-equilibrium moiré phenomena at the atomic scale.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Neutron-neutron scattering length from the 6 He(p,pα)nn reaction

We propose a novel method to measure the neutron-neutron scattering length using the 6 He(p,pα)nn reaction in inverse kinematics at high energies. The method is based on the final-state interaction (FSI) between the neutrons after the sudden knockout of the α particle. We show that the details of the neutron-neutron relative-energy distribution allow for a precise extraction of the s-wave scattering length. Here, we present the state of the art in regard to the theory of this distribution. The distribution is calculated in two steps. First, we calculate the ground-state wave function of 6 He as a αnn three-body system. For this purpose we use Halo effective field theory, which also provides uncertainty estimates for the results. We compare our results at this stage to model calculations done with the computer code face. In a second step we determine the effects of the nn FSI using the nn t-matrix. We compare these FSI results to approximate FSI approaches based on standard FSI enhancement factors. While the final distribution is sensitive to the nn scattering length, it depends only weakly on the effective range. Throughout we emphasize the impact of theoretical uncertainties on the neutron-neutron relative-energy distribution, and discuss the extent to which those uncertainties limit the extraction of the neutron-neutron scattering length from the reaction 6 He(p,pα)nn.

6 ≤ A ≤ 19↗
DOE OSTI2026

Discovery of van Hove singularities: electronic fingerprints of 3Q magnetic order in a van der Waals quantum magnet

Magnetically intercalated transition metal dichalcogenides are emerging as a rich platform for exploring exotic quantum states in van der Waals magnets. Among them, Co x TaS 2 has attracted intense interest following the recent discovery of a distinctive 3Q magnetic ground state and a pronounced topological Hall effect below a critical doping of x ≈ 1/3, both intimately tied to cobalt concentration. To date, direct signatures of this enigmatic 3Q magnetic order in the electronic structure remain elusive. Here we report a comprehensive doping dependent angle resolved photoemission spectroscopy study that unveils these long-sought fingerprints. Our data reveal an unexpected inverse-Mexican-hat dispersion along the K-M-K' direction, accompanied by two van Hove singularities. These features are consistent with theoretical predictions for a 3Q magnetic order near three-quarters band filling on a cobalt triangular lattice. These results provide evidence of 3Q magnetic order in the electronic structure, establishing TMD van der Waals magnets as tunable materials to explore the interplay between magnetism and topology.

Luo, Hai-Lan [University of California, Berkeley, ↗
DOE OSTI2023

Photochemistry sample sticks for inelastic neutron scattering

Every material experiences atomic and molecular motions that are generally termed vibrations in gases and liquids or phonons in solid state materials. Optical spectroscopy techniques, such as Raman, infrared absorption spectroscopy, or inelastic neutron scattering (INS), can be used to measure the vibrational/phonon spectrum of ground state materials properties. A variety of optical pump probe spectroscopies enable the measurement of excited states or elucidate photochemical reaction pathways and kinetics. So far, it has not been possible to study photoactive materials or processes in situ using INS due to the mismatch between neutron and photon penetration depths, differences between the flux density of photons and neutrons, cryogenic temperatures for INS measurements, vacuum conditions, and a lack of optical access to the sample space. These experimental hurdles have resulted in very limited photochemistry studies using INS. Here we report on the design of two different photochemistry sample sticks that overcome these experimental hurdles to enable in situ photochemical studies using INS, specifically at the VISION instrument at Oak Ridge National Laboratory. We demonstrate the use of these new measurement capabilities through (1) the in situ photodimerization of anthracene and (2) the in situ photopolymerization of a 405 nm photoresin using 405 nm excitation as simple test cases. Furthermore, these new measurement apparatus broaden the science enabled by INS to include photoactive materials, optically excited states, and photoinitiated reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗