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Results for “Electronic Correlations”

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.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Electronic correlation induced expansion of Fermi pockets in δ-plutonium

Plutonium is a critically important material as the behavior of its 5f electrons stands midway between the metalliclike itinerant character of the light actinides and localized atomic-core-like character of the heavy actinides. The δ phase of plutonium (δ-Pu), whereas still itinerant, has a large coherent Kondo peak and strong electronic correlations coming from its near-localized character. Here, using sophisticated Gutzwiller wave function and dynamical mean-field theory correlated theories, we study the Fermi surface and associated mass renormalizations of δ-Pu together with calculations of the de Haas–van Alphen frequencies. We find a large (~200%) correlation induced volume expansion in both the hole and the electron pockets of the Fermi surface in addition to an intermediate mass enhancement. All of the correlated electron theories predict, approximately, the same hole pocket placement in the Brillouin zone, which is different from that obtained in conventional density-functional band-structure theory, whereas the electron pockets from all theories are in, roughly, the same place.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Role of Electron Correlation beyond the Active Space in Achieving Quantitative Predictions of Spin-Phonon Relaxation

Single-molecule magnets (SMMs) are promising candidates for molecular-scale data storage and processing due to their strong magnetic anisotropy and long spin relaxation times. However, as temperature rises, interactions between electronic states and lattice vibrations accelerate spin relaxation, significantly limiting their practical applications. Recently, ab initio simulations have made it possible to advance our understanding of phonon-induced magnetic relaxation, but significant deviations from experiments have often been observed. The description of molecules’ electronic structure has been mostly based on complete active space self-consistent field (CASSCF) calculations, and the impact of electron correlation beyond the active space remains largely unexplored. In this study, we provide the first systematic investigation of spin-phonon relaxation in SMMs with post-CASSCF multiconfigurational methods, specifically CAS followed by second-order perturbation theory and multiconfiguration pair-density functional theory. Taking Co(II)- and Dy(III)-based SMMs as case studies, we analyze how electron correlation influences spin-phonon relaxation rates across a range of temperatures, comparing theoretical predictions with experimental observations. Our findings demonstrate that post-CASSCF treatments make it possible to achieve quantitative predictions for Co(II)-based SMMs. For Dy(III)-based systems, however, accurate predictions require consideration of additional effects, underscoring the urgent necessity of further advancing the study of the effects of electronic correlation in these complex systems.

Energy↗
DOE OSTI2022

Assessing MP2 frozen natural orbitals in relativistic correlated electronic structure calculations

The high computational scaling with the basis set size and the number of correlated electrons is a bottleneck limiting applications of coupled cluster algorithms, in particular for calculations based on two- or four-component relativistic Hamiltonians, which often employ uncontracted basis sets. This problem may be alleviated by replacing canonical Hartree–Fock virtual orbitals by natural orbitals (NOs). Here, in this paper, we describe the implementation of a module for generating NOs for correlated wavefunctions and, in particular, second order Møller–Plesset perturbation frozen natural orbitals (MP2FNOs) as a component of our novel implementation of relativistic coupled cluster theory for massively parallel architectures [Pototschnig et al. J. Chem. Theory Comput. 17, 5509, (2021)]. Our implementation can manipulate complex or quaternion density matrices, thus allowing for the generation of both Kramers-restricted and Kramers-unrestricted MP2FNOs. Furthermore, NOs are re-expressed in the parent atomic orbital (AO) basis, allowing for generating coupled cluster singles and doubles NOs in the AO basis for further analysis. By investigating the truncation errors of MP2FNOs for both the correlation energy and molecular properties—electric field gradients at the nuclei, electric dipole and quadrupole moments for hydrogen halides HX (X = F–Ts), and parity-violating energy differences for H 2 Z 2 (Z = O–Se)—we find MP2FNOs accelerate the convergence of the correlation energy in a roughly uniform manner across the Periodic Table. It is possible to obtain reliable estimates for both energies and the molecular properties considered with virtual molecular orbital spaces truncated to about half the size of the full spaces.

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

On the role of dynamic electron correlation in non-orthogonal configuration interaction with fragments

Two different approaches have been implemented to include the effect of dynamic electron correlation in the Non-Orthogonal Configuration Interaction for Fragments (NOCI-F) method. The first is based on shifting the diagonal matrix elements of the NOCI matrix, while the second incorporates the dynamic correlation explicitly in the fragment wave functions used to construct the many-electron basis functions of the NOCI. The two approaches are illustrated for the calculation of the electronic coupling relevant in singlet fission and the coupling of spin moments in organic radicals. Comparison of the calculated diabatic couplings, the NOCI energies and wave functions shows that dynamic electron correlation is not only efficiently but also effectively incorporated by the shifting approach and can largely affect the coupling between electronic states. Additionally, it brings the NOCI coupling of the spin moments in close agreement with benchmark calculations.

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

Electron correlations in the ${H_{c2}}$ of FeySe$_{1-x}$Sx (0.10 $\leqslant x\leqslant$ 0.24, $y\geqslant$ 0.9)

In this work, we report on the evolution of the electronic correlation strength across the nematic critical point in FeySe$_{1-x}$Sx ($0.10\leqslant x \leqslant0.24; y \geqslant0.9$), inferred from the measurements of the slope of the upper critical field $H_{c2}$. Superconducting transition T c and quasiparticle mass $m^*$ exhibit similar reduction with sulfur content x. Our results indicate that electronic correlations from all Fermi surface pockets show strong interconnection with pairing strength and are not governed by the change of nematic fluctuations. The upper critical field anisotropy γH = $H_{c2}^{ab}$/$H_{c2}^c$ exhibits a minimum in the critical region and stronger temperature dependence away from it.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Enhanced superconductivity and electron correlations in intercalated ZrTe 3

We report charge density waves (CDWs) with superconductivity, competing Fermi surface instabilities, and collective orders have captured much interest in two-dimensional van der Waals (vdW) materials. Understanding the CDW suppression mechanism, its connection to the emerging superconducting state, and electronic correlations provides opportunities for engineering the electronic properties of vdW heterostructures and thin-film devices. Using a combination of the thermal transport, x-ray photoemission spectroscopy, Raman measurements, and first-principles calculations, we observe an increase in electronic correlations of the conducting states as the CDW is suppressed in ZrT e3 with 5% Cu and Ni intercalation in the vdW gap. As superconductivity emerges, intercalation brings not only decoupling of quasi-one-dimensional conduction electrons with phonons as a consequence of intercalation-induced lattice expansion but also a drastic increase in Zr 2+ at the expense of Zr 4+ metal atoms. These observations not only demonstrate the potential of atomic intercalates in the vdW gap for ground-state tuning but also illustrate the crucial role of the Zr metal valence in the formation of collective electronic orders.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Suppression of thermal conductivity and electronic correlations in Fe 1– x Ru x Sb 2 (0 ≤ x ≤ 0.6)

We present simultaneous suppression of FeSb 2 thermal conductivity and electronic correlations in Fe 1– x Ru x Sb 2 (0 ≤ x ≤ 0.6) single crystal alloys. Small energy gap Δ 1 in Kondo-insulator-like semiconductor FeSb 2 associated with impurity in-gap state increases whereas the intrinsic bandgap Δ 2 decreases upon Ru substitution on Fe atomic site. Thermopower is suppressed along with the intrinsic bandgap and with the thermal conductivity. The more delocalized 4 d character of atomic orbital of Ru brings suppression of electronic correlations, but also an increase in impurity density which reduces phonon mean free path and surface scattering length. Our results indicate a range of Ru doping x where nanostructuring could be used to suppress thermal conductivity further, potentially toward the amorphous limit.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Gate control of electron correlations towards Mott field effect transistors (MottFET)

The modulation of channel conductance in field-effect transistors (FETs) via metal-insulator-semiconductor structures has revolutionized information processing and storage. However, the limitations of silicon-based FETs in electrical switching have driven the search for new materials capable of overcoming these constraints. Electrostatic gating of competing electronic phases in a Mott material near its metal-to-insulator transition (MIT) offers the prospects of substantial modulation of the conducting electrons and electrical resistivity through small changes in band filling. While electrostatic control of the MIT has been previously reported, the advancement of Mott materials toward novel Mott-based transistors, MottFETs requires the realization of their unique physical properties in a solid-state device. In this study, we present gate control of electron correlation using a solid-state device utilizing the oxide Mott system La 1-x Sr x VO 3 as a correlated FET channel. We report on a gate resistance response that cannot be explained in a purely electrostatic framework. This behavior suggests an enhancement in effective mass and a reduction in effective carrier density as the system approaches its insulating state, consistent with theoretical predictions for Mott systems, suggesting at least 100× charge gain originating from the correlated behavior. These preliminary results pave the way toward the development of highly efficient, low-power electronic devices that could surpass the performance bottlenecks of conventional FETs by leveraging the electronic phase transitions of correlated electron systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Ultrafast Electron Correlations and Memory Effects at Work: Femtosecond Demagnetization in Ni

Experimental observations of the ultrafast (less than 50 fs) demagnetization of Ni have so far defied theoretical explanations particularly since its spin-flipping time is much less than that resulting from spin-orbit and electron-lattice interactions. Through the application of an approach that benefits from spin-flip time-dependent density-functional theory and dynamical mean-field theory, we show that proper inclusion of electron correlations and memory (time dependence of electron-electron interaction) effects leads to demagnetization at the femtosecond scale, in good agreement with experimental observations. Furthermore, our calculations reveal that this ultrafast demagnetization results mainly from spin-flip transitions from occupied to unoccupied orbitals implying a dynamical reduction of exchange splitting. In this work, these conclusions are found to be valid for a wide range of laser pulse amplitudes. They also pave the way for ab initio investigations of ultrafast charge and spin dynamics in a variety of quantum materials in which electron correlations may play a definitive role.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Evidence for strong electronic correlations in the bulk state of grey arsenic

Here, we investigate the electron band structure of grey arsenic, whose (111) face hosts the topological Shockley state. Interestingly, the bulk band close to the touching point with the surface state exhibits the characteristics of inelastic scattering. Moreover, the band structure analysis reveals linearity in the imaginary part of electron self-energy. These features are analogous to those observed in high-temperature superconductors and marginal Fermi liquid systems, respectively, where strong electronic correlations exist. Our results suggest that correlated many-body states can be connected by non-interacting topological states, providing a viable playground to explore the coupling between topological and correlated states via grey arsenic surface.

ARPES↗
DOE OSTI2020

Nanoscale Conductivity Imaging of Correlated Electronic States in WSe 2 /WS 2 Moiré Superlattices

We report the nanoscale conductivity imaging of correlated electronic states in angle-aligned WSe 2 /WS 2 heterostructures using microwave impedance microscopy. Here, the noncontact microwave probe allows us to observe the Mott insulating state with one hole per moiré unit cell that persists for temperatures up to 150 K, consistent with other characterization techniques. In addition, we identify for the first time a Mott insulating state at one electron per moiré unit cell. Appreciable inhomogeneity of the correlated states is directly visualized in the hetero-bilayer region, indicative of local disorders in the moiré superlattice potential or electrostatic doping. Our work provides important insights on 2D moiré systems down to the microscopic level.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Electronic correlations in the semiconducting half-Heusler compound FeVSb

Electronic correlations are crucial to the low-energy physics of metallic systems with localized d and f states; however, their effect on band insulators and semiconductors is typically negligible. Here, we measure the electronic structure of the half-Heusler compound FeVSb, a band insulator with a filled shell configuration of 18 valence electrons per formula unit ( s 2 p 6 d 10 ). Additionally, angle-resolved photoemission spectroscopy reveals a mass renormalization of m * / m bare = 1.4 , where m * is the measured effective mass and m bare is the mass from density functional theory calculations with no added on-site Coulomb repulsion. Our measurements are in quantitative agreement with dynamical mean-field theory calculations, highlighting the many-body origin of the mass renormalization. This mass renormalization lies in dramatic contrast to other filled shell intermetallics, including the thermoelectric materials CoTiSb and NiTiSn, and has a similar origin to that in FeSi, where Hund's coupling induced fluctuations across the gap can explain a dynamical self-energy and correlations. Our work calls for a rethinking of the role of correlations and Hund's coupling in intermetallic band insulators.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Magnetic Topological Semimetal Phase with Electronic Correlation Enhancement in SmSbTe

The ZrSiS family of compounds hosts various exotic quantum phenomena due to the presence of both topological nonsymmorphic Dirac fermions and nodal-line fermions. In this material family, the LnSbTe (Ln = lanthanide) compounds are particularly interesting owing to the intrinsic magnetism from magnetic Ln which leads to new properties and quantum states. Here in this work, the authors focus on the previously unexplored compound SmSbTe. The studies reveal a rare combination of a few functional properties in this material, including antiferromagnetism with possible magnetic frustration, electron correlation enhancement, and Dirac nodal-line fermions. These properties enable SmSbTe as a unique platform to explore exotic quantum phenomena and advanced functionalities arising from the interplay between magnetism, topology, and electronic correlations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Intertwined charge, spin, and orbital degrees of freedom under electronic correlations in the one-dimensional Fe 3+ chalcogenide chain

Motivated by recent developments in the study of quasi-one-dimensional iron systems with Fe 2+ , we comprehensively study an Fe 3+ chalcogenide chain system. Based on first-principles calculations, the Fe 3+ chain has a similar electronic structure to that discussed before for the Fe 2+ chain, because of the similar Fe⁢𝑋 4 (𝑋 = S or Se) tetrahedron-chain geometry. Furthermore, a three-orbital electronic Hubbard model for this chain was constructed using the density matrix renormalization group method. A robust antiferromagnetic coupling was unveiled in the chain direction. In addition, in the intermediate electronic correlation 𝑈/𝑊 region, we found an interesting orbital-selective Mott phase with the coexistence of localized and itinerant electrons (𝑈 is the on-site Hubbard repulsion, while 𝑊 is the electronic bandwidth) based on the orbital-selective behavior observed in the charge fluctuations. Furthermore, we do not observe any obvious pairing tendency in the Fe 3+ chain in the electronic-correlation 𝑈/𝑊 region, where superconducting pairing tendencies were reported before in iron ladders. This suggests that superconductivity is unlikely to emerge in the Fe 3+ systems. Finally, our results clearly establish the similarities and differences between Fe 2+ and Fe 3+ iron chains, as well as iron ladders.

density matrix renormalization group↗
DOE OSTI2021

Revealing the nature of electron correlation in transition metal complexes with symmetry breaking and chemical intuition

Here, in this work, we provide a nuanced view of electron correlation in the context of transition metal complexes, reconciling computational characterization via spin and spatial symmetry breaking in single-reference methods with qualitative concepts from ligand-field and molecular orbital theories. These insights provide the tools to reliably diagnose the multi-reference character, and our analysis reveals that while strong (i.e., static) correlation can be found in linear molecules (e.g., diatomics) and weakly bound and antiferromagnetically coupled (monometal-noninnocent ligand or multi-metal) complexes, it is rarely found in the ground-states of mono-transition-metal complexes. This leads to a picture of static correlation that is no more complex for transition metals than it is, e.g., for organic biradicaloids. In contrast, the ability of organometallic species to form more complex interactions, involving both ligand-to-metal σ-donation and metal-to-ligand π-backdonation, places a larger burden on a theory's treatment of dynamic correlation. We hypothesize that chemical bonds in which inter-electron pair correlation is non-negligible cannot be adequately described by theories using MP2 correlation energies and indeed find large errors vs experiment for carbonyl-dissociation energies from double-hybrid density functionals. A theory's description of dynamic correlation (and to a less important extent, delocalization error), which affects relative spin-state energetics and thus spin symmetry breaking, is found to govern the efficacy of its use to diagnose static correlation.

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

Thermoelectricity and electronic correlation enhancement in FeS by light Se doping

We report thermoelectric studies of FeS 1–x Se x (x = 0, 0.06) superconducting single crystals that feature high irreversibility fields and critical current density J c comparable to materials with much higher superconducting critical temperatures (T c 's). The ratio of T c to the Fermi temperature T F is very small, indicating weak electronic correlations. With a slight selenium substitution on sulfur site in FeS both T c /T F and the effective mass m* rise considerably, implying increase in electronic correlation of the bulk conducting states. The first-principle calculations show rise of the density of states at the Fermi level in FeS 0.94 Se 0.06 when compared to FeS, which is related not only to Fe but also to chalcogen-derived electronic states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗