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At least 541 records · Page 30

Ferromagnetic order beyond the superconducting dome in a cuprate superconductor

According to conventional wisdom, the extraordinary properties of the cuprate high-temperature superconductors arise from doping a strongly correlated antiferromagnetic insulator. The highly overdoped cuprates—whose doping lies beyond the dome of superconductivity—are considered to be conventional Fermi liquid metals. We report the emergence of itinerant ferromagnetic order below 4 kelvin for doping beyond the superconducting dome in thin films of electron-doped La 2– x Ce x CuO 4 (LCCO). The existence of this ferromagnetic order is evidenced by negative, anisotropic, and hysteretic magnetoresistance, hysteretic magnetization, and the polar Kerr effect, all of which are standard signatures of itinerant ferromagnetism in metals. This surprising result suggests that the overdoped cuprates are strongly influenced by electron correlations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Modeling Absolute Redox Potentials of Ferrocene in the Condensed Phase

Absolute thermodynamic quantities for critical chemical reactions are needed to determine the role of solvents and reactive environments in catalysis and electrocatalysis beyond the relative scales typically employed. In principle, theoretical methods can provide such quantification but are often hindered by the innate complexity of strong electron correlation and dynamic relaxation of solvent environments. Here, we present and validate a protocol for calculating the redox potentials of ferrocene/ferrocenium redox pair in the acetonitrile. Equation-of-motion ionization potential coupled-cluster single-double (EOM-IP-CCSD) and effective fragment potential (EFP) methods are used to characterize the adiabatic and vertical ionization potentials (IP) as well as the electron affinity processes. We benchmark molecular mechanics against the EFP model to show the differences in ferrocene electronic polarizability in two redox states. Our best estimate of the redox potential (4.94 eV) agrees well with the experimental value (4.93 eV). This demonstrated the ability of modern computational methods to predict absolute redox potentials quantitatively and, more critically, quantify the correlation of dynamic effects, which underlie their origin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Orbital selective Kondo effect in heavy fermion superconductor UTe2

Abstract Heavy fermion systems emerge from the collective Kondo effect, and their superconductivity can serve as a promising platform for realizing next-generation quantum technologies. However, it has been a great challenge to explore many-body effects in heavy fermion systems with ab-initio approaches. We computed the electronic structure of UTe 2 without purposive judgements, such as intentional selection of on-site Coulomb interaction and disregarding spin-orbit coupling. We show that U-5 f electrons are highly localized in the paramagnetic normal state, giving rise to the Kondo effect. It is also found that the hybridization between U-5 f and U-6 d predominantly in the orthorhombic a b -plane is responsible for the high-temperature Kondo effect. In contrast, the hybridization between U-5 f and Te-5 p along the c -axis manifests the Kondo scattering at a much lower temperature, which could be responsible for the low-temperature upturn of the c -axis resistivity. Our results show that the electron correlation in UTe 2 is orbital selective, which naturally elucidates the recent experimental observations of anomalous temperature dependence of resistivity. Furthermore, we suggest that the Kondo effect is suppressed at high pressure owing to weak localization of magnetic moments, which results from enhanced U-5 f electron hopping. Our discovery provides significant insight toward understanding anisotropic quantum behavior including selective re-entrant superconductivity in heavy fermion UTe 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electronic anisotropy and rotational symmetry breaking at a Weyl semimetal/spin ice interface

In magnetic pyrochlore materials, the interplay of spin-orbit coupling, electronic correlations, and geometrical frustration gives rise to exotic quantum phases, including topological semimetals and spin ice. While these phases have been observed in isolation, the interface-driven phenomena emerging from their interaction have never been realized previously. Here, we report on the discovery of interfacial electronic anisotropy and rotational symmetry breaking at a heterostructure consisting of the Weyl semimetal Eu 2 Ir 2 O 7 and spin ice Dy 2 Ti 2 O 7 . Subjected to magnetic fields, we unveil a sixfold anisotropic transport response that is theoretically accounted by a Kondo-coupled heterointerface, where the spin ice’s field-tuned magnetism induces electron scattering in the Weyl semimetal’s topological Fermi-arc states. Furthermore, at elevated magnetic fields, we reveal a twofold anisotropic response indicative of the emergence of a symmetry-broken many-body state. This discovery showcases the potential of pyrochlore frustrated magnet/topological semimetal heterostructures in search of emergent interfacial phenomena.

Science & Technology - Other Topics↗

Electron Transfer Theory Elucidates the Hidden Role Played by Triethylamine and Triethanolamine during Photocatalysis

Triethylamine (TEA) and triethanolamine (TEOA) are renowned, in part, for their ability to reductively quench excited states by outer-sphere electron transfer with vast and still growing applications as sacrificial electron donors for photocatalytic systems. Upon amine oxidation, the resulting TEA •+ and TEOA •+ radical cations undergo proton transfer (or hydrogen atom transfer), resulting in the formation of a chemical reductant that has an α-carbon centered radical adjacent to the nitrogen center (TEA • and TEOA • ). In this contribution, we have electrochemically and spectroscopically characterized a set of electron acceptors which, upon accepting an electron, are a series of photocatalysts, [ReCl(R 1 R 2 -bpy)(CO) 3 ] •– , where R 1 and R 2 are electron-donating and electron-withdrawing groups in the 4,4′- and 5,5′-positions on the bipyridyl ligand. Here, we substantiated the formation of the electron donors, TE(O)A • , by spin trapping electron paramagnetic resonance spectroscopy, where TE(O)A • reacts with 2,4,6-tri-tert-butylnitrosobenzene to generate N-centered and O-centered radical adducts. Having established the chemical behaviors of the electron acceptors and donors individually, the electron transfer rate constants were determined across a 1.43 V range in driving force. The redox potential of TEA • was benchmarked to within ±80 mV on an absolute scale in V vs Fc + /Fc in CH 3 CN by using an empirical rate vs free-energy correlation, electron transfer theory, and density functional theory calculations. The equilibrium potentials for TEA • and TEOA • were determined to be −1.98 V and −1.76 V, respectively. Based on the kinetic and thermochemical analysis presented for TEA • and TEOA • , these transient radicals can be broadly considered strong homogeneous chemical reductants within the wider context of photoredox potentials. Thus, this work clarifies a frequently unnoticed secondary function for these sacrificial electron donors during photocatalysis and rationalizes the possibility of a one-photon/two-electron conversion process that is dependent on the free-energy exchange between TE(O)A • and photocatalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Bond length alternation of π -conjugated polymers predicted by the Fermi–Löwdin orbital self-interaction correction method

π-conjugated polymers have been used in a wide range of practical applications, partly due to their unique properties that originate in the delocalization of electrons through the polymer backbone. The level of delocalization can be characterized by the induced bond length alternation (BLA), with shorter BLA connected with strong delocalization and vice versa. The accurate description of this structural parameter can be considered a benchmark for testing the capability of different electronic structure methods for self-interaction error (SIE) removal and electron correlation inclusion. Density functional theory (DFT), in its local or semi-local flavors, suffers from SIE and, thus, underestimates the BLA compared to self-interaction-free methods. In this work, we utilize the Fermi–Löwdin orbital self-interaction correction (FLOSIC) method for one-electron self-interaction removal to characterize the BLA of five oligomers with increasing length extrapolated to the polymeric limit. We compare the self-interaction-free BLA to several DFT approximations, Møller–Plesset second-order perturbation theory (MP2), and the BLA obtained with the domain based local pair natural orbital CCSD(T) [DLPNO-CCSD(T)] approximation. Our findings show that FLOSIC corrects for the small BLA given by (semi-)local DFT approximations, but it tends to overcorrect with respect to CAM-B3LYP, MP2, and DLPNO-CCSD(T).

Chemistry↗

Mixed Cu-simple metal dimers and trimers - CuLi, CuLi2, CuNa, CuK, CuBe, CuBe2, Cu2Be, CuAl, and CuAl2

Theoretical studies of selected diatomic and triatomic molecules containing copper and the simple metals Li, Na, K, Be, and Al are presented, with emphasis on elucidating the nature of the bonding in mixed transition metal-simple metal systems. Large Gaussian basis sets are used in the diatomic calculations, and are used to calibrate the triatomic calculations, in which somewhat smaller Gaussian basis sets are employed. Electron correlation is incorporated using both the single-reference singles plus doubles configuration interaction and coupled pair functional methods. It is found that alkali atoms form very polar sigma bonds with copper, and that the ionicity increases with the inclusion of higher excitations because they improve the electron affinity of copper, which in turn allows a larger negative charge on copper. Aluminum is found to form stronger bonds than beryllium, since it does not have to undergo sp hybridization. Some of the trimers bond by forming three-center three-electron bonds. These multicenter bonds are quite strong even when compared to the two-electron bonds in the dimers or to other bonding mechanisms in the trimers.

Bauschlicher, Charles W., Jr.↗

Status and Challenges of Density Functional Theory

Here, we discuss some of the challenges facing density functional theory (DFT) and recent progress in DFT for both ground and excited electronic states. We discuss key aspects of the results we have been able to obtain with the strategy of designing density functionals to have various ingredients and functional forms that are then optimized to accurately predict various types of properties and systems with as much universality as possible. Finally, we make specific recommendations of approximate density functionals that are well suited for particular kinds of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron confinement–induced plasmonic breakdown in metals

Plasmon resonance represents the collective oscillation of free electron gas density and enables enhanced light-matter interactions in nanoscale dimensions. Traditionally, the classical Drude model describes plasmonic excitation, wherein plasma frequency exhibits no spatial dispersion. Here, we show conclusive experimental evidence of the breakdown of plasmon resonance and a consequent metal-insulator transition in an ultrathin refractory plasmonic material, hafnium nitride (HfN). Epitaxial HfN thick films exhibit a low-loss and high-quality Drude-like plasmon resonance in the visible spectral range. However, as the film thickness is reduced to nanoscale dimensions, Coulomb interaction among electrons increases because of electron confinement, leading to the spatial dispersion of plasma frequency. With a further decrease in thickness, electrons lose their ability to shield the incident electric field, turning the medium into a dielectric. The observed metal-insulator transition might carry some signatures of Wigner crystallization and indicates that such transdimensional, between 2D and 3D, films can serve as a promising playground to study strongly correlated electron systems.

Science & Technology - Other Topics↗

UOTe: Kondo‐Interacting Topological Antiferromagnet in a Van der Waals Lattice

Since the initial discovery of 2D van der Waals (vdW) materials, significant effort has been made to incorporate the three properties of magnetism, band structure topology, and strong electron correlations—to leverage emergent quantum phenomena and expand their potential applications. However, the discovery of a single vdW material that intrinsically hosts all three ingredients has remained an outstanding challenge. Here, in this work, the discovery of a Kondo-interacting topological antiferromagnet is reported in the vdW 5f electron system UOTe. It has a high antiferromagnetic (AFM) transition temperature of 150 K, with a unique AFM configuration that breaks the combined parity and time reversal (PT) symmetry in an even number of layers while maintaining zero net magnetic moment. This angle-resolved photoemission spectroscopy (ARPES) measurements reveal Dirac bands near the Fermi level, which combined with the theoretical calculations demonstrate UOTe as an AFM Dirac semimetal. Within the AFM order, the presence of the Kondo interaction is observed, as evidenced by the emergence of a 5ƒ flat band near the Fermi level below 100 K and hybridization between the Kondo band and the Dirac band. The density functional theory calculations in its bilayer form predict UOTe as a rare example of a fully-compensated AFM Chern insulator.

36 MATERIALS SCIENCE↗

Topological Electronic Structure Evolution with Symmetry Breaking Spin Reorientation in (Fe 1–x Co x )Sn

Topological materials hosting kagome lattices have drawn considerable attention due to the interplay between topology, magnetism, and electronic correlations. The (Fe 1–x Co x )Sn system not only hosts a kagome lattice but has a tunable symmetry-breaking magnetic moment with temperature and doping. In this study, angle-resolved photoemission spectroscopy and first-principles calculations are used to investigate the interplay between the topological electronic structure and varying magnetic moment from the planar to axial antiferromagnetic phases. Here, evidence for a theoretically predicted gap at the Dirac point is revealed in the low-temperature axial phase, but no gap opening is observed across a temperature-dependent magnetic phase transition. However, topological surface bands are observed to shift in energy as the surface magnetic moment is reduced or becomes disordered over time during experimental measurements. The shifting surface bands may preclude the determination of a temperature-dependent bulk gap, but this highlights the intricate connections between magnetism and topology with a surface/bulk dichotomy that can affect material properties and their interrogation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Type-II Weyl nodes, flat bands, and evidence for a topological Hall-effect in the new ferromagnet FeCr 3 Te 6

The interplay between linearly dispersing, or Dirac-like, and flat electronic bands, for instance, in the kagome ferromagnets, has attracted attention due to a possible interplay between topology and electronic correlations. Here, we report the synthesis, structural, electrical, and magnetic properties of a single-crystalline ferromagnetic compound, namely Fe 1/3 ⁢CrTe 2 or FeCr 3 ⁢Te 6 , which crystallizes in the 𝑃$\overline{3}$⁢𝑚⁢1 space group instead of the 𝐼⁢2/𝑚 previously reported for FeCr 2 ⁢Te 4 . Electronic band structure calculations reveal type-II Dirac nodes and relatively flat bands near the Fermi level (ε 𝐹 ). This compound shows onset Curie temperature 𝑇 c ≃ 120K, followed by an additional ferromagnetic transition near 𝑇 c2 ∼ 92.5K. Below 𝑇 c , FeCr 3 ⁢Te 6 displays a pronounced anomalous Hall effect, as well as sizable coercive fields that exceed 𝜇 0 ⁢𝐻=1 T at low 𝑇⁢s. However, a scaling analysis indicates that the anomalous Hall effect results from a significant intrinsic contribution, as expected from the calculations, and also from the extrinsic mechanism, i.e., scattering. The extrinsic contribution probably results from occupational disorder at the 1b Fe-site within the van der Waals gap of the CrTe 2 host. We also observe evidence for a topological Hall component superimposed onto the overall Hall response, suggesting the presence of chiral spin textures akin to skyrmions in this centrosymmetric system. Their possible presence will require experimental confirmation.

36 MATERIALS SCIENCE↗

Mapping charge excitations in generalized Wigner crystals

Transition metal dichalcogenide-based moiré superlattices exhibit strong electron-electron correlations, thus giving rise to strongly correlated quantum phenomena such as generalized Wigner crystal states. Evidence of Wigner crystals in transition metal dichalcogenide moire superlattices has been widely reported from various optical spectroscopy and electrical conductivity measurements, while their microscopic nature has been limited to the basic lattice structure. Theoretical studies predict that unusual quasiparticle excitations across the correlated gap between upper and lower Hubbard bands can arise due to long-range Coulomb interactions in generalized Wigner crystal states. However, the microscopic proof of such quasiparticle excitations is challenging because of the low excitation energy of the Wigner crystal. Here, in this study, we describe a scanning single-electron charging spectroscopy technique with nanometre spatial resolution and single-electron charge resolution that enables us to directly image electron and hole wavefunctions and to determine the thermodynamic gap of generalized Wigner crystal states in twisted WS 2 moiré heterostructures. High-resolution scanning single-electron charging spectroscopy combines scanning tunnelling microscopy with a monolayer graphene sensing layer, thus enabling the generation of individual electron and hole quasiparticles in generalized Wigner crystals. We show that electron and hole quasiparticles have complementary wavefunction distributions and that thermodynamic gaps of ~50 meV exist for the 1/3 and 2/3 generalized Wigner crystal states in twisted WS 2 .

36 MATERIALS SCIENCE↗

Higher-order Van Hove singularities in kagome topological bands

Motivated by the growing interest in band structures featuring higher-order Van Hove singularities (HOVHS), we investigate a spinless fermion kagome system characterized by nearest-neighbor (NN) and next-nearest-neighbor (NNN) hopping amplitudes. While NN hopping preserves time-reversal symmetry, NNN hopping, akin to chiral hopping on the Haldane lattice, breaks time-reversal symmetry and leads to the formation of topological bands with Chern numbers ranging from 𝐶 = ±1 to ±4. We perform analytical and numerical analysis of the energy bands near the high-symmetry points Γ, ±𝐊, and 𝐌 𝑖 (𝑖 = 1, 2, and 3), which uncover a rich and complex landscape of HOVHS, controlled by the magnitude and phase of the NNN hopping. We observe power-law divergences in the density of states (DOS), 𝜌⁡(𝜀)∼|𝜀| −𝜈 , with exponents 𝜈 = 1/2, 1/3, 1/4, which can significantly affect the anomalous Hall response at low temperatures when the Fermi level crosses the HOVHS. Additionally, the NNN hopping induces the formation of higher Chern number bands 𝐶 = ±2, ±4 in the middle of the spectrum obeying a sublattice interference whereupon electronic states are maximally localized in each of the sublattices when the momentum approaches the three high-symmetry points 𝐌 𝑖 (𝑖 = 1, 2, and 3) on the Brillouin zone boundary. Finally, this classification of HOVHS in kagome systems provides a platform to explore unconventional electronic orders induced by electronic correlations.

Chern insulators↗

Shot noise and universal Fano factor as a characterization of strongly correlated metals

Shot noise measures out-of-equilibrium current fluctuations and is a powerful tool to probe the nature of current-carrying excitations in quantum systems. Recent shot-noise measurements in the heavy-fermion strange metal YbRh 2 Si 2 exhibit a strong suppression of the Fano factor ( F )—the ratio of the current noise to the average current in the dc limit. This system is representative of metals in which electron correlations are extremely strong. Here we carry out the first theoretical study on the shot noise of diffusive metals in the regime of strong correlations. A Boltzmann-Langevin equation formulation is constructed in a quasiparticle description in the presence of strong correlations. We find that F = 3 / 4 in such a correlation regime. Thus, we establish the aforementioned Fano factor as universal to Fermi liquids, and we show that the Fano factor suppression observed in experiments on YbRh 2 Si 2 necessitates a loss of the quasiparticles. Our work opens the door to systematic theoretical studies of shot noise as a means of characterizing strongly correlated metallic phases and materials. Published by the American Physical Society 2024

Wang, Yiming (ORCID:0000000277582921)↗

Theoretical predictive screening of noble-metal-containing M 3 AuC 2 (M = Ti, V, and Cr) MAX phases

Using first-principles density functional theory (DFT), the ground state physical properties of the newly synthesized noble-metal-containing Ti 3 AuC 2 MAX phase have been investigated. The effect of transition-element Ti replacement (V and Cr) on physical properties, including structural, elastic, electronic, thermal, and optical are presented. The optimized lattice parameters of Ti 3 AuC 2 MAX phase are in good agreement with the experimental values and decrease when we replace Ti with V and then Cr. The magnetic properties of M 3 AuC 2 are predicted by using generalized gradient approximation (GGA) incorporating onsite electron correlation parameter (Hubbard U parameter) within DFT. Out of three studied MAX phases, V 3 AuC 2 and Cr 3 AuC 2 phases exhibit magnetism. The thermodynamical stability of M 3 AuC 2 (M = Ti, V, and Cr) phases is discussed by the formation enthalpy with respect to their most competing phases. The electronic structure reveals that these phases have metallic nature and are electrically anisotropic. The M-element replacement has an effect on the bonding properties of M 3 AuC 2 . The bonding between M-C is in the order of Cr 3 AuC 2 > V 3 AuC 2 > Ti 3 AuC 2 according to their peak positions and heights of density of states in the occupied site, which is also confirmed from the charge density distribution. The elastic properties indicate that M 3 AuC 2 phases are ductile, machinable, less stiff, and better resistant to thermal shock and are elastically anisotropic. To understand the properties of M 3 AuC 2 for the extreme environment, we employed a quasi-harmonic Debye model at the pressure and temperature range of 0–50 GPa and 0–1600 K, respectively. Additionally, we evaluated thermal conductivity and melting temperature to further understand the potential of these MAX phases in coating applications at elevated temperature. In relation to optical properties, these MAX phases have a reasonable absorption coefficient in the visible as well as in the ultra-violet regions. The reflectivity of M 3 AuC 2 phases is polarization dependent and of 45 % against the visible region, which reveals its potential as coating material to minimize solar heating.

312 MAX phases↗

Theoretical study of the crystal and electronic properties of α - RuI 3

The material α-RuCl 3 , with a two-dimensional Ru honeycomb sublattice, has attracted considerable attention because it may be a realization of the Kitaev quantum spin liquid. Recently, a new honeycomb material, α-RuCl 3 , was prepared under moderately high pressure, and it is stable under ambient conditions. However, different from α-RuCl 3 , α-RuI 3 was reported to be a paramagnetic metal without long-range magnetic order down to 0.35 K. Here, the structural and electronic properties of the quasi-two-dimensional α-RuI 3 are theoretically studied. First, based on first-principles density functional theory calculations, the ABC stacking honeycomb-layer R$\bar{3}$ (No. 148) structure is found to be the most likely stacking order for α-RuI 3 along the c axis. Furthermore, both R$\bar{3}$ and P$\bar{3}$1c are dynamically stable because no imaginary frequency modes were obtained in the phononic dispersion spectrum without Hubbard U. Moreover, the different physical behavior of α-RuI 3 compared to α-RuCl 3 can be understood naturally. The strong hybridization between Ru 4d and I 5p orbitals decreases the “effective” atomic Hubbard repulsion, leading the electrons of RuI3 to be less localized than in RuCl 3 . As a consequence, the effective electronic correlation is reduced from Cl to I, leading to the metallic nature of α-RuI 3 . Based on the DFT+U (Ueff=2 eV) plus spin-orbital coupling, we obtained a spin-orbit Mott insulating behavior for α-RuCl 3 and, with the same procedure, a metallic behavior for α-RuI 3 , in good agreement with experimental results. Furthermore, when introducing large (unrealistic) U eff =6 eV, the spin-orbit Mott gap opens in α-RuI 3 as well, supporting the physical picture we are proposing. Our results provide guidance to experimentalists and theorists working on two-dimensional transition metal tri-iodide layered materials.

2-dimensional systems↗

Quantum Spin Torque Driven Transmutation of an Antiferromagnetic Mott Insulator

The basic model of spin-transfer torque (STT) in antiferromagnetic spintronics considers the exchange of angular momentum between quantum spins of flowing electrons and noncollinear-to-them localized spins treated as classical vectors. These vectors are assumed to realize Néel order in equilibrium, ↑ ↓ ∙∙∙ ↑ ↓, and their STT-driven dynamics is described by the Landau-Lifshitz-Gilbert (LLG) equation. However, many experimentally employed materials (such as archetypal NiO) are strongly electron-correlated antiferromagnetic Mott insulators (AFMIs) whose localized spins form a ground state quite different from the unentangled Néel state | ↑ ↓ ∙∙∙ ↑ ↓$\rangle$. The true ground state is entangled by quantum spin fluctuations, leading to the expectation value of all localized spins being zero, so that LLG dynamics of classical vectors of fixed length rotating due to STT cannot even be initiated. Instead, a fully quantum treatment of both conduction electrons and localized spins is necessary to capture the exchange of spin angular momentum between them, denoted as quantum STT. We use a recently developed time-dependent density matrix renormalization group approach to quantum STT to predict how injection of a spin-polarized current pulse into a normal metal layer coupled to an AFMI overlayer via exchange interaction and possibly small interlayer hopping—mimicking, e.g., topological-insulator/NiO bilayer employed experimentally—will induce a nonzero expectation value of AFMI localized spins. This new nonequilibrium phase is a spatially inhomogeneous ferromagnet with a zigzag profile of localized spins. The total spin absorbed by AFMI increases with electron-electron repulsion in AFMIs, as well as when the two layers do not exchange any charge.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗