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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Ab Initio Study of Atomic and Electronic Structure of Promising Ba4XMn3O12 (X = Nb, Ce, Pr) Oxides for Solar Thermochemical Hydrogen Production

The two-step metal oxide water-splitting cycle is one of the most viable approach for Solar Thermochemical Hydrogen (STCH) production. Challenges exist in finding suitable oxides that can satisfy thermodynamics of the STCH redox cycle under viable range of temperatures and partial pressures. Recently, BXM family members, i.e., Ba4NbMn3O12 (BNM), Ba4CeMn3O12 (BCM), Ba4PrMn3O12 (BPM) are discovered to exhibit promising STCH performance. However, the magnetic degrees of freedom of their experimental crystal structures is not characterized, and only hypothetical models exist for their electronic structure. We performed Monte-Carlo sampling for the magnetic spin arrangement of Mn atoms to provide explicit atomic structure models for their ground state 12R polytype and determined the most stable spin configuration for each member after structure relaxation using density functional theory (DFT) calculations. We also elucidate the most stable charge configuration (Mn3+/Mn4+ arrangement) for BNM among the existing hypothesis in literature. We investigate these strongly correlated oxides using different levels of theory (DFT+U, Hybrid-DFT) to develop better understanding of their electronic structure. These calculations allowed us to develop a model based on molecular orbital interactions that help explain the observed changes in their experimental x-ray spectroscopy measurements. Thereby, help link differences in electronic structure of BXM family members to their varying water-splitting behavior. These structure models will further facilitate future in-depth defect studies to model STCH redox cycle of these oxides.

atomic and magnetic structure↗
DOE OSTI2020

Charge transfer rate constants for the carotenoid-porphyrin-C 60 molecular triad dissolved in tetrahydrofuran: The spin-boson model vs the linearized semiclassical approximation

Charge transfer rate constants were calculated for the carotenoid-porphyrin-C 60 (CPC 60 ) molecular triad dissolved in explicit tetrahydrofuran. The calculation was based on mapping the all-atom anharmonic Hamiltonian of this system onto the spin-boson Hamiltonian. The mapping was based on discretizing the spectral density from the time correlation function of the donor–acceptor potential energy gap, as obtained from all-atom molecular dynamics simulations. Different spin-boson Hamiltonians were constructed for each of the possible transitions between the three excited electronic states in two different triad conformations. The rate constants of three possible transitions were calculated via the quantum-mechanically exact Fermi’s golden rule (FGR), as well as a progression of more approximate expressions that lead to the classical Marcus expression. The advantage of the spin-boson approach is that once the mapping is established, the quantum-mechanically exact FGR and the hierarchy of approximations are known in closed form. The classical Marcus charge transfer rate constants obtained with the spin-boson Hamiltonians were found to reproduce those obtained from all-atom simulations with the linearized semiclassical approximation, thereby confirming the equivalence of the two approaches for this system. Furthermore, within the spin-boson Hamiltonian, we also found that the quantum-mechanically exact FGR rate constants were significantly enhanced compared to the classical Marcus theory rate constants for two out of three transitions in one of the two conformations under consideration. The results confirm that mapping to the spin-boson model can yield accurate predictions for charge transfer rate constants in a system as complex as CPC 60 dissolved in tetrahydrofuran.

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

Equilibrium Dynamics of Infinite-Range Quantum Spin Glasses in a Field

We determine the low-energy spectrum and Parisi replica-symmetry-breaking function for the spin-glass phase of the quantum Ising model with infinite-range random exchange interactions and transverse and longitudinal ( h ) fields. We show that, for all h , the spin-glass state has full replica symmetry breaking and the local spin spectrum is gapless, with a spectral density that vanishes linearly with frequency. These results are obtained using an action functional—argued to yield exact results at low frequencies—that expands in powers of a spin-glass order parameter, which is bilocal in time, and a matrix in replica space. We also present the exact solution of the infinite-range spherical quantum p -rotor model at nonzero h : here, the spin-glass state has one-step replica symmetry breaking and gaplessness only appears after imposition of an additional marginal stability condition. Possible connections to experiments on random arrays of trapped Rydberg atoms are noted. Published by the American Physical Society 2024

Tikhanovskaya, Maria↗
DOE OSTI2024

Hydrogen Bonding Analysis of Structural Transition-Induced Symmetry Breaking and Spin Splitting in a Hybrid Perovskite Employing a Synergistic Diffraction-DFT Approach

Two-dimensional (2D) hybrid organic–inorganic perovskites (HOIPs) offer an outstanding opportunity for spin-related technologies owing in part to their tunable structural symmetry breaking and distortions driven by organic–inorganic hydrogen (H) bonds. However, understanding how H-bonds tailor inorganic symmetry and distortions and therefore enhance spin splitting for more effective spin manipulation remains imprecise due to challenges in measuring H atom positions using X-ray diffraction. Here, we report a thermally induced structural transition (at ~209 K) for a 2D HOIP, (2-BrPEA) 2 PbI 4 [2-BrPEA = 2-(2-bromophenyl)ethylammonium], which induces inversion asymmetry and a strong spin splitting (ΔE > 30 meV). While X-ray diffraction generally establishes heavy atom coordinates, we utilize neutron diffraction for accurate H atom position determination, demonstrating that the structural transition-induced rearrangement of H-bonds with distinct bond strengths asymmetrically shifts associated iodine atom positions. Further, consequences of this shift include an increased structural asymmetry, an enhanced difference between adjacent interoctahedra distortions (i.e., Pb–I–Pb bond angles), and therefore significant spin splitting. We further show that H-only density-functional theory (DFT) relaxation of the X-ray structure shifts H atoms to positions that are consistent with the neutron experimental data, validating a convenient pathway to more generally improve upon HOIP H-bonding analyses derived from quicker/less-expensive X-ray data.

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

Advances and Challenges of SCAN and r 2 SCAN Density Functionals in Transition‐Metal Compounds

ABSTRACT Transition‐metal compounds (TMCs) with open‐shell d ‐electrons are characterized by a complex interplay of lattice, charge, orbital, and spin degrees of freedom, giving rise to various fascinating applications. Often exhibiting exotic properties, these compounds are commonly classified as correlated systems due to strong inter‐electronic interactions called Hubbard U . This inherent complexity presents significant challenges to Kohn‐Sham density functional theory (KS‐DFT), the most widely used electronic structure method in condensed matter physics and materials science. While KS‐DFT is, in principle, exact for the ground‐state total energy, its exchange‐correlation energy must be approximated in practice. The mean‐field nature of KS implementations, combined with the limitations of current exchange‐correlation density functional approximations, has led to the perception that DFT is inadequate for correlated systems, particularly TMCs. Consequently, a common workaround involves augmenting DFT with an on‐site Hubbard‐like U correction. In recent years, the strongly constrained and appropriately normed (SCAN) density functional, along with its refined variant r 2 SCAN, has achieved remarkable progress in accurately describing the structural, energetic, electronic, magnetic, and vibrational properties of TMCs, challenging the traditional perception of DFT's limitations. This review explores the design principles of SCAN and r 2 SCAN, highlights their key advancements in studying TMCs, explains the mechanisms driving these improvements, and addresses the remaining challenges in this evolving field.

Zhang, Yubo [Minjiang Collaborative Center for The↗
DOE OSTI2022

Sign-free determinant quantum Monte Carlo study of excitonic density orders in a two-orbital Hubbard-Kanamori model

While excitonic instabilities in multiorbital systems recently have come under scrutiny in a variety of transition-metal compounds, understanding emergence of these instabilities from strong electronic interactions has remained a challenge. In this work, we present a sign-problem-free determinant quantum Monte Carlo study of excitonic density orders in a half-filled two-orbital Hubbard-Kanamori model with broken orbital degeneracy, which accounts for the role of Hund's coupling in transition-metal compounds. For strong inverted (negative) Hund's exchange, we find numerical evidence for the emergence of excitonic density order, with competition between anti-ferro-orbital order and Q = (π, π) excitonic density order as a function of orbital splitting and Hund's coupling. While inverted Hund's coupling stabilizes a spin-singlet excitonic density phase for weak orbital splitting, positive Hund's coupling favors a spin-triplet excitonic density phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Oxygen magnetic polarization, nodes in spin density, and zigzag spin order in oxides

Recent studies on Ba 2 CoO 4 (BCO) and SrRuO 3 (SRO) have unveiled a variety of intriguing phenomena, such as magnetic polarization on oxygens, unexpected nodes in the spin density profile along bonds, and unusual zigzag spin patterns in triangular lattices. Here, using simple model calculations supplemented by density functional theory we explain the presence of nodes based on the antibonding character of the dominant singly occupied molecular orbitals along the transition metal (TM) to oxygen bonds. Our simple model also allows us to explain the net polarization on oxygen as originated from the hybridization between atoms and mobility of the electrons with spins opposite to those of the closest TM atoms. Overall, our results are not limited to BCO and SRO, but they are generic and qualitatively predict the net polarization expected on any ligands, according to the spin order of the closest TM atoms and the number of intermediate ligand atoms. Finally, we propose that a robust easy-axis anisotropy would suppress the competing 120° antiferromagnetic order to stabilize the zigzag pattern order as ground state in a triangular lattice. Our generic predictions should be applicable to any other compound with characteristics similar to those of BCO and SRO.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Understanding the origin of magneto-crystalline anisotropy in pure and Fe/Si substituted SmCo 5

In this paper, we report magneto-crystalline anisotropy of pure and Fe/Si substituted SmCo5. The calculations were performed using the advanced density functional theory (DFT) including onsite electron-electron correlation and spin-orbit coupling. Si substitution substantially reduces both the uniaxial magnetic anisotropy and the magnetic moment. Fe substitution with the selective site, on the other hand, enhances the magnetic moment with a limited chemical stability. The magnetic hardness of the SmCo5 is governed by the Sm 4f localized orbital contribution. The 4f density of states (DOS) becomes flat and split with the substitution of Co (2c) with Si/Fe atoms, except with the Fe substitution at 3 g sites. It is also confirmed that Si substitution favors the thermodynamic stability on contrary to the diminished magnetic and anisotropic effects in SmCo5 at either sites.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Magnetic Ni-N-Ni Centers in N-substituted NiO

Here, to explore how anion substitution modifies the existing magnetism in strongly correlated oxides, we investigate local electronic states and magnetic ordering in nickel oxide (NiO) induced by substituting oxygen (O) with nitrogen (N). Each N introduces an additional N 2p hole and modifies the magnetic moment of a neighboring nickel (Ni) cation site, as the exchange interaction between this hole and the Ni $e_{g}$ electrons exceeds the Ni-O-Ni superexchange interaction. This leads to the formation of Ni-N-Ni centers consisting of five spins, without perturbing the antiferromagnetic NiO lattice. These centers are studied using density functional theory and confirmed through high-resolution spectroscopy on N-substituted NiO thin films grown by molecular beam epitaxy. This type of magnetic design may enable future advances in quantum technologies based on strongly correlated materials, such as quantum sensors and spin-based qubits.

Godin, Simon [Univ. of British Columbia, Vancouver↗
DOE OSTI2020

Spatial decomposition of magnetic anisotropy in magnets: Application to doped Fe 16 N 2

We propose a scheme of decomposition of the total relativistic energy in solids to intra- and interatomic contributions. The method is based on a site variation of such fundamental constant as the speed of light. As a practical illustration of the method, we tested such decomposition in the case of a spin-orbit interaction variation for the decomposition of the magnetic anisotropy energy (MAE) in CoPt. We further studied the α" - Fe 16 N 2 magnet doped by Bi, Sb, Co, and Pt atoms. It was found that the addition of Pt atoms can enhance the MAE by as much as five times while Bi and Sb substitutions double the total MAE. Using the proposed technique, we demonstrate the spatial distribution of these enhancements. Our studies also suggest that Sb, Pt, and Co substitutions could be synthesized by experiments.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Effective spin-mixing conductance of topological-insulator/ferromagnet and heavy-metal/ferromagnet spin-orbit-coupled interfaces: A first-principles Floquet-nonequilibrium Green function approach

The spin-mixing conductance (SMC) is a key quantity determining efficiency of spin transport across interfaces. Thus, knowledge of its precise value is required for accurate measurement of parameters quantifying numerous effects in spintronics, such as spin-orbit torque, spin Hall magnetoresistance, spin Hall effect, and spin pumping. However, the standard expression for SMC, provided by the scattering theory in terms of the reflection probability amplitudes, is inapplicable when strong spin-orbit coupling (SOC) is present directly at the interface. This is the precisely the case of topological-insulator/ferromagnet and heavy-metal/ferromagnet interfaces of great contemporary interest. We introduce an approach where first-principles Hamiltonian of these interfaces, obtained from noncollinear density functional theory (ncDFT) calculations, is combined with charge-conserving Floquet-nonequilibrium-Green-function formalism to compute directly the pumped spin current $I^{S_z}_L$ into semi-infinite left lead of two-terminal heterostructures Cu/X/Co/Cu or Y/Co/Cu—where X = Bi 2 Se 3 and Y = Pt or W—due to microwave-driven steadily precessing magnetization of the Co layer. This allows us to extract an effective SMC as a prefactor in $I^{S_z}_L$ versus precession cone angle θ dependence, as long as it remains the same, $I^{S_z}$ ∝ sin 2 θ , as in the case where SOC is absent. By comparing calculations where SOC in switched off versus switched on in ncDFT calculations, we find that SOC consistently reduces the pumped spin current and therefore the effective SMC.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Competing itinerant and local spin interactions in kagome metal FeGe

The combination of a geometrically frustrated lattice, and similar energy scales between degrees of freedom endows two-dimensional Kagome metals with a rich array of quantum phases and renders them ideal for studying strong electron correlations and band topology. The Kagome metal, FeGe is a noted example of this, exhibiting A-type collinear antiferromagnetic (AFM) order at T N ≈ 400 K, then establishes a charge density wave (CDW) phase coupled with AFM ordered moment below T CDW ≈ 110 K, and finally forms a c-axis double cone AFM structure around T Canting ≈ 60 K. Here we use neutron scattering to demonstrate the presence of gapless incommensurate spin excitations associated with the double cone AFM structure of FeGe at temperatures well above T Canting and T CDW that merge into gapped commensurate spin waves from the A-type AFM order. Commensurate spin waves follow the Bose factor and fit the Heisenberg Hamiltonian, while the incommensurate spin excitations, emerging below T N where AFM order is commensurate, start to deviate from the Bose factor around T CDW , and peaks at T Canting . This is consistent with a critical scattering of a second order magnetic phase transition with decreasing temperature. By comparing these results with density functional theory calculations, we conclude that the incommensurate magnetic structure arises from the nested Fermi surfaces of itinerant electrons and the formation of a spin density wave order.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effects of chemical disorder and spin-orbit coupling on the electronic-structure and Fermi-surface topology of YbSb-based monopnictides

Here, in this work, we study the influence of disorder on the electronic structure of YbSb—a rare-earth monopnictide featuring a simple rocksalt (B1) crystal structure and a well-defined Fermi-surface topology—by employing first-principles density-functional theory. We focus on chemical disorder introduced through Te and Al doping, selected based on their thermodynamic stability in alloyed configurations, to understand how such perturbations modify the electronic states of YbSb. Our results indicate that Te doping predominantly introduces electronlike states at the 𝑋 and 𝐿 points, while Al doping leads to a suppression of holelike states at Γ, effectively driving the system from a semimetallic state to one characterized by very narrow-gap behavior at Γ. This modulation of the Fermi surface, particularly the reduction of central hole pockets at Γ, plays a central role in altering interpocket scattering—a mechanism critical for tuning quantum transport properties, including superconductivity. This disorder-driven modulation of the Fermi surface, particularly the suppression of central hole pockets at Γ, controls interpocket scattering, which is essential for optimizing quantum transport properties, including superconductivity. Our results show that disorder can be effectively used for engineering band topology, thereby tuning quantum related response through a tailored electronic structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

DFT calculations and theory do not support enantiospecificity in NMR J-coupling constants

Distinguishing the enantiomers of small organic molecules is an industrially relevant problem with important implications for the health of the population. In a recent publication, Bouchard and co-workers have suggested that large differences in indirect spin-spin (J) coupling constants between enantiomers are possible. A close inspection of their work revealed significant flaws in their density functional theory (DFT) calculations and that the reported effects disappear with appropriate care. We thus conclude that enantiospecificity in spin-spin coupling constants has not be demonstrated either experimentally or theoretically.

Perras, Frédéric A. [Ames Laboratory (AMES), Ames,↗
DOE OSTI2025

Exploring the Coexistence of Spin States in [Fe(tpy-Ph) 2 ] 2+ Complexes on Au(111) Using DFT Calculations

In this work, we systematically study the electronic structure and stability of spin states of the [Fe-(tpy-ph) 2 ] 2+ molecule in both the gas phase and on a Au(111) substrate using density functional theory + U (DFT+ U ) calculations. We find that the stability of the Fe 2+ ion’s spin states predicted by the computations is significantly influenced by the Hubbard U parameter. In the gas phase, the low-spin (LS, S = 0) state is found to be energetically favorable for U (Fe) ≤ 3 eV, whereas the high-spin (HS, S = 2) state is stabilized for U (Fe) > 3 eV. Interaction with the Au(111) substrate is found to elevate the critical U for the spin-state transition to 3.5 eV. Additionally, we perform L-edge X-ray absorption spectroscopy (XAS) calculations for both HS and LS states. The calculated XAS suggests that the HS state more closely aligns with the experimental observations, indicating the potential coexistence of the HS state as the initial state during the X-ray excitation process. These findings enrich our understanding of spin-state dynamics in [Fe(tpy-Ph) 2 ] 2+ .

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

Hybridized kagome bands and induced Ti magnetism in RTi3Bi4 (R = Nd, Sm, Gd) kagome metals studied using angle-resolved photoemission spectroscopy and x-ray magnetic circular dichroism

Kagome materials are known for hosting emergent quantum phenomena driven by the interaction between different lattice, charge and spin orders. Here, we present a detailed angle resolved photoemission (ARPES), density functional theory (DFT) and x-ray magnetic circular dichroism (XMCD) study of the electronic and magnetic structure of RTi3Bi4 (R = Nd, Sm, Gd). ARPES and DFT demonstrate that the bulk electronic band structure is dominated by the hybridization of the Ti bands, and the weak electron-like pocket at Γ is identified as a surface state. The isotropic XAS profile of the M 4,5-edge of the rare earth is consistent with the presence of R 3+ oxidation state. Using the XMCD sum rules, backed by the atomic multiplet theory calculations, we obtain the spin and orbital magnetic moments. The Ti L2,3-edge XMCD reveals the presence of a small magnetic moment in GdTi3Bi4, presumably driven by the proximity of the Ti kagome layers to the zigzag chains of Gd, while the total magnetic moment of Gd is shared by the f and d electrons. Our combined XMCD, ARPES and DFT study brings an important piece of information to understand the spin flip transitions and anomalous Hall effect observed in the RTi3Bi4 kagome metals.

Lim, C.↗
DOE OSTI2025

Large critical fields in superconducting Ti 4 ⁢Ir 2⁢ O from spin-orbit coupling

The recently synthesized 𝜂-carbide-type superconductors exhibit large critical fields. A notable example is Ti 4 ⁢Ir2⁢ O, for which the upper critical field strongly violates the Pauli paramagnetic limit, a behavior that is unusual for cubic materials that preserve inversion symmetry. Here, by combining density functional theory (DFT) and analytic modeling, we provide an explanation for this enhanced Pauli limiting field. We show that the nonsymmorphic Fd⁢-3 ⁢m symmetry implies that the electronic states near the X points exhibit strong spin-orbit coupling (SOC), which leads to a vanishing effective 𝑔 factor and enables the enhanced Pauli limiting field. Furthermore, our DFT results reveal a Van Hove singularity peak near the X points, accounting for ∼65% of the total density of states (DOS), occurring near the chemical potential. We propose that the strong SOC and enhanced DOS in the vicinity of the X points provide the origin of the observed enhancement of the critical field. This leads to a prediction that the magnetic field will lead to a strongly momentum-dependent gap suppression. As a result, the gap due to electronic states away from (near to) the X points will be rapidly (slowly) suppressed by fields.

Critical field↗
DOE OSTI2022

Competitive effects of glucan’s main hydrolysates on biochar formation: A combined experiment and density functional theory analysis

We report the complexity of polysaccharide hydrothermal products increases the difficulty of exploring the formation of biochar, limiting the development of biochar. This work clarifies the completive effects of glucan’s main hydrolysates on biochar formation from three aspects: experimental, thermodynamic, and kinetic. The products distribution illustrates that 5-HMF, FA, and LA are mainly involved in the formation of biochar. Biochar mainly includes furan ring, ether group, and ester group by the analysis of magic-angle-spinning nuclear magnetic resonance, X-ray photoelectron spectroscopy, and elemental analysis. Combined experiments and density functional theory analysis, the etherification reaction of 5-HMF itself is most likely to occur and is key to form biochar, followed by the esterification of FA with 5-HMF, and then the etherification of 5-HMF and LA. The further verified experiments also manifest these results. This work will develop a foundation for exploring the complex formation mechanism of cellulose-based biochar.

59 BASIC BIOLOGICAL SCIENCES↗