Order Spin Orbit Research Articles

Imprinted atomic displacements drive spin–orbital order in a vanadate perovskite

AbstractPerovskites with the generic composition ABO3 exhibit an enormous variety of quantum states, such as orbital order, magnetism and superconductivity. Their flexible and comparatively simple structure allows for straightforward chemical substitution and cube-on-cube combination of different compounds in atomically sharp epitaxial heterostructures. Many of the diverse physical properties of perovskites are determined by small deviations from the ideal cubic perovskite structure, which are challenging to control. Here we show that directional imprinting of atomic displacements in the antiferromagnetic Mott insulator YVO3 can be achieved by depositing epitaxial films on different facets of the same isostructural substrate. These facets were chosen such that other well-known control parameters, including lattice and polarity mismatch with the overlayer, remain nearly unchanged. We observe signatures of staggered orbital and magnetic order and demonstrate distinct spin–orbital ordering patterns on different facets. We attribute these results to the influence of specific octahedral rotation and cation displacement patterns, which are imprinted by the substrate facet, on the covalency of the bonds and the superexchange interactions in YVO3. Our results show that substrate-induced templating of lattice distortion patterns constitutes a pathway for materials design beyond established strain-engineering strategies.

Quantum fundaments of catalysis: true electronic potential energy.

Catalysis is a quantum phenomenon enthalpically driven by electronic correlations with many-particle effects in all of its branches, including electro-photo-catalysis and electron transfer. This means that only probability amplitudes provide a complete relationship between the state of catalysis and observations. Thus, in any atomic system material), competing space-time electronic interactions coexist to define its (related) properties such as stability, (super)conductivity, magnetism (spin-orbital ordering), chemisorption and catalysis. Catalysts, reactants, and chemisorbed and transition states have the possibility of optimizing quantum correlations to improve reaction kinetics. Active sites with closed-shell orbital configurations share a maximum number of spin-paired electrons, mainly optimizing coulombic attractions and covalency and defining weakly correlated closed-shell (WCCS) structures. However, in compositions with open-shell orbital configurations, at least, quantum spin exchange interactions (QSEIopenshells) arise, stabilising unpaired electrons in less covalent bonds and differentiating non-weakly (or strongly) correlated open-shell (NWCOS) systems. In NWCOS catalysts, electronic ground states can have bonds with diverse and rival spin-orbital orderings as well as ferro-, ferri- and multiple antiferro-magnetic textures, which deeply define their activities. Particularly in inter-atomic ferromagnetic (FM) bonds, the increase in relevance of non-classical quantum potentials can significantly optimize chemisorption energies, transition states (TSs), activation energies (overpotential) and spin-dependent electron transfer (conductivity), overall implying the need for explaining the thermodynamic and kinetic origin of catalysis from its true quantum electronic energy. To do so, we use the connection between the Born-Oppenheimer approximation and Virial theorem in the treatment of electronic kinetic and potential energies. Thus, the exact fundamental interactions that decompose TSs appear. The possibility of increasing the stabilization of TSs, due to quantum correlations on NWCO catalysts, opens the possibility of simultaneously reducing chemisorption enthalpies and activation barriers of reaction mechanisms, which implies the anticipation and explanation of positive deviations from the Brønsted-Evans-Polanyi principle.

Efficient magnetic switching in a correlated spin glass

The interplay between spin-orbit interaction and magnetic order is one of the most active research fields in condensed matter physics and drives the search for materials with novel, and tunable, magnetic and spin properties. Here we report on a variety of unique and unexpected observations in thin multiferroic Ge1−xMnxTe films. The ferrimagnetic order parameter in this ferroelectric semiconductor is found to switch direction under magnetostochastic resonance with current pulses many orders of magnitude lower as for typical spin-orbit torque systems. Upon a switching event, the magnetic order spreads coherently and collectively over macroscopic distances through a correlated spin-glass state. Utilizing these observations, we apply a novel methodology to controllably harness this stochastic magnetization dynamics.

Spin-orbital order and excitons in magnetoresistive HoBi

The rare-earth monopnictides $R\phantom{\rule{0}{0ex}}X$ have been found to exhibit exotic topological three-dimensional states, coupled to unique magnetotransport responses such as extreme magnetoresistance. These findings generated interest to understand the interplay between electronic band topology, transport, and magnetism in $R\phantom{\rule{0}{0ex}}X$. While neutron scattering is indispensable to fully characterize magnetism, there is very little modern work on this family of compounds. Since the details of the magnetism have a profound impact on the electronic band topology and transport in materials, the authors present here a thorough characterization of the magnetism in HoBi, based on modern neutron scattering techniques.

Discovery of a Magnetic Dirac System with a Large Intrinsic Nonlinear Hall Effect.

Magnetic materials exhibiting topological Dirac fermions are attracting significant attention for their promising technological potential in spintronics. In these systems, the combined effect of the spin-orbit coupling and magnetic order enables the realization of novel topological phases with exotic transport properties, including the anomalous Hall effect and magneto-chiral phenomena. Herein, we report experimental signature of topological Dirac antiferromagnetism in TaCoTe2 via angle-resolved photoelectron spectroscopy and first-principles density functional theory calculations. In particular, we find the existence of spin-orbit coupling-induced gaps at the Fermi level, consistent with the manifestation of a large intrinsic nonlinear Hall conductivity. Remarkably, we find that the latter is extremely sensitive to the orientation of the Néel vector, suggesting TaCoTe2 as a suitable candidate for the realization of non-volatile spintronic devices with an unprecedented level of intrinsic tunability.

Long-range spin-orbital order in the spin-orbital SU(2)×SU(2)×U(1) model

By using the tensor-network state algorithm, we study a spin-orbital model with SU(2)$\times$SU(2)$\times$U(1) symmetry on the triangular lattice. This model was proposed to describe some triangular $d^1$ materials and was argued to host a spin-orbital liquid ground state. In our work the trial wavefunction of its ground state is approximated by an infinite projected entangled simplex state and optimized by the imaginary-time evolution. Contrary to the previous conjecture, we find that the two SU(2) symmetries are broken, resulting in a stripe spin-orbital order with the same magnitude $m=0.085(10)$. This value is about half of that in the spin-1/2 triangular Heisenberg antiferromagnet. Our result demonstrates that although the long-sought spin-orbital liquid is absent in this model the spin-orbital order is significantly reduced due to the enhanced quantum fluctuation. This suggests that high-symmetry spin-orbital models are promising in searching for exotic states of matter in condensed-matter physics.

Impact of the electric field on isotropic and anisotropic spin Hamiltonian parameters.

One may obviously think that the best way to control magnetic properties relies on using a magnetic field. However, it is not convenient to focus a magnetic field on a small object, whereas it is much easier to do so with an electric field. Magnetoelectric coupling allows one to control the magnetization with the electric field and the polarization with the magnetic field and could therefore provide a solution to this problem. This paper aims at quantifying the impact of the electric field on both the isotropic magnetic exchange and the Dzyaloshinskii-Moriya interaction in the case of a binuclear system of S = 1/2 spins. This study follows previous studies that showed that very high Dzyaloshinskii-Moriya interaction, i.e., the antisymmetric exchange, can be generated when close to first order spin orbit coupling. We will, therefore, explore this regime in a model Cu(II) complex that exhibits a quasi-degeneracy of the dx2-y2 and dxy orbitals. This situation is indeed the one that allows us to obtain the largest spin orbit couplings in transition metal complexes. We will show that both the magnetic exchange and the Dzyaloshinskii-Moriya interaction are very sensitive to the electric field and that it would therefore be possible to modulate and control magnetic properties by the electric field. Finally, rationalizations of the obtained results will be proposed.

Non-Aufbau orbital ordering and spin density modulation in high-spin donor-acceptor conjugated polymers.

High-spin ground-state organic materials with unique spin topology can significantly impact molecular magnetism, spintronics, and quantum computing devices. However, strategies to control the spin topology and alignment of the unpaired spins in different molecular orbitals are not well understood. Here, we report modulating spin distribution along the molecular backbone in high-spin ground-state donor-acceptor (D-A) conjugated polymers. Density functional theory calculations indicate that substitution of different heteroatoms (such as C, Si, N, and Se) alters the aromatic character in the thiadiazole unit of the benzobisthiadiazole (BBT) acceptor and modulates the oligomer length to result in high-spin triplet ground-state, orbital and spin topology. The C, Si, and Se atom substituted polymers show a localized spin density at the two opposite ends of the polymers. However, a delocalized spin distribution is observed in the N substituted polymer. We find that the hybridization (sp3vs. sp2) of the substituent atom plays an important role in controlling the electronic structure of these materials. This study shows that atomistic engineering is an efficient technique to tune the spin topologies and electronic configurations in the high-spin ground-state donor-acceptor conjugated polymers, compelling synthetic targets for room-temperature magnetic materials.

Doped spin–orbital Mott insulators: Orbital dilution versus spin–orbital polarons

Here we compare two kinds of doping in transition metal oxides by considering defects due to the substitution of the transition metal or rare earth element. The focus is on insulating t2g orbital systems and we present various mechanisms that lead to reorganization of spin–orbital order. Substitutional doping of d4-transition metal by d3 ions generally results in removal of the local orbital degrees of freedom and the exchange on hybrid d4−d3 bonds modifying locally (or globally) spin–orbital order. Different routes of rearrangement of spin–orbital patterns are also found when considering doping by d2 ions. Here we demonstrate that in the regime of strong impurity-host coupling ferro-orbital type ordering is favored. This analysis can find application to ruthenate oxides with Mn or Cr replacing the Ru atoms. In contrast, charged (Sr,Ca) defect replacing R ion in the R1−x(Ca,Sr)xVO3 (R=La,Y) perovskites generates a spin–orbital polaron in the defect cube. We show that t2g orbital rotations are then induced near the charged defect and a doped hole disturbs orbital order. As a result, the collapse of G-type orbital order occurs but C-AF spin order stays robust under increasing doping.

Doping-Induced Quantum Spin Hall Insulator to Superconductor Transition.

A quantum spin Hall insulating state that arises from spontaneous symmetry breaking has remarkable properties: skyrmion textures of the SO(3) order parameter carry charge 2e. Doping this state of matter opens a new route to superconductivity via the condensation of skyrmions. We define a model amenable to large-scale negative sign free quantum MonteCarlo simulations that allows us to study this transition. Our results support a direct and continuous doping-induced transition between the quantum spin Hall insulator and an s-wave superconductor. We can resolve dopings away from half-filling down to δ=0.0017. Such routes to superconductivity have been put forward in the realm of twisted bilayer graphene.

Controlling in-gap end states by linking nonmagnetic atoms and artificially-constructed spin chains on superconductors

Chains of magnetic atoms with either strong spin-orbit coupling or spiral magnetic order which are proximity-coupled to superconducting substrates can host topologically non-trivial Majorana bound states. The experimental signature of these states consists of spectral weight at the Fermi energy which is spatially localized near the ends of the chain. However, topologically trivial Yu-Shiba-Rusinov in-gap states localized near the ends of the chain can lead to similar spectra. Here, we explore a protocol to disentangle these contributions by artificially augmenting a candidate Majorana spin chain with orbitally-compatible nonmagnetic atoms. Combining scanning tunneling spectroscopy with ab-initio and tight-binding calculations, we realize a sharp spatial transition between the proximity-coupled spiral magnetic order and the non-magnetic superconducting wire termination, with persistent zero-energy spectral weight localized at either end of the magnetic spiral. Our findings open a new path towards the control of the spatial position of in-gap end states, trivial or Majorana, via different chain terminations, and the realization of designer Majorana chain networks for demonstrating topological quantum computation.

Hidden spin-orbital hexagonal ordering induced by strong correlations in LiVS2

We present a first-principles many-body analysis of multi-orbital lattice susceptibilities in the metallic phase of the quasi-twodimensional compound LiVS$_2$. We base this on advanced correlated electronic structure methods for the $t_{2g}$-shell to reveal a highly entangled spin-orbital hexagonal ordering (SOHO) bringing about an inherently intersite order parameter for the trimerization transition, which eventually leads to an intriguing insulating phase at low temperature.

Enhancing NMR Quantum Computation by Exploring Heavy Metal Complexes as Multiqubit Systems: A Theoretical Investigation.

Assembled together with the most common qubits used in nuclear resonance magnetic (NMR) quantum computation experiments, spin-1/2 nuclei, such as 113Cd, 199Hg, 125Te, and 77Se, could leverage the prospective scalable quantum computer architectures, enabling many and heteronuclear qubits for NMR quantum information processing (QIP) implementations. A computational design strategy for prescreening recently synthesized complexes of cadmium, mercury, tellurium, selenium, and phosphorus (called MRE complexes) as suitable qubit molecules for NMR QIP is reported. Chemical shifts and spin-spin coupling constants (SSCCs) in five MRE complexes were examined using the spin-orbit zeroth order regular approximation (ZORA) at the density functional theory level and the four-component relativistic Dirac-Kohn-Sham approach. In particular, the influence of different conformers, basis sets, exchange-correlation functionals, and methods to treat the relativistic as well as solvent effects were studied. The differences in the chemical shifts and SSCCs between different low energy conformers of the studied complexes were found to be very small. The TZ2P basis set was found to be the optimum choice for the studied chemical shifts, while the TZ2P-J basis set was the best for the couplings studied in this work. The PBE0 exchange-correlation functional exhibited the best performance for the studied MRE complexes. The addition of solvent effects has not improved on the gas phase results in comparison to the experiment, with the exception of the phosphorus chemical shift. The use of MRE complexes as qubit molecules for NMR QIP could face the challenges in single qubit control and multiqubit operations. They exhibit chemical shifts appropriately dispersed, allowing qubit addressability and exceptionally large spin-spin couplings, which could reduce the time of quantum gate operations and likely preserve the coherence.

Current induced chiral domain wall motion in CuIr/CoFeB/MgO thin films with strong higher order spin–orbit torques

We investigate the Dzyaloshinskii–Moriya interaction (DMI) and spin–orbit torque effects in CuIr/CoFeB/MgO heterostructures. To this end, harmonic Hall measurements and current induced domain wall motion experiments are performed. The motion of domain walls at zero applied field due to current demonstrates the presence of DMI in this system. We determine the strength of the DMI to be D=+5 ± 3 μJ/m2 and deduce right-handed chirality in domain walls showing a partial Néel type spin structure. To ascertain the torques, we perform a second harmonic measurement to quantify the damping- and field-like current induced effective fields as a function of the magnetization direction. From the angular dependent analysis, we identify non-negligible higher order terms for polar magnetization angles θ>0, which need to be included when considering the effective manipulation of spins by current.

Analytic solutions to compact binary inspirals with leading order spin-orbit contribution using the dynamical renormalization group

We calculate the real-space trajectory and spin precession of a generic spinning compact binary inspiral at any time instant using the dynamical renormalization group formalism. This method leads to closed-form analytic solutions to the binary motion through treating radiation reaction as perturbations and resumming the secular growth of perturbative terms. We consider the spin-orbit effects at leading order and the 2.5PN radiation reaction without orbit averaging or precession averaging for arbitrary individual masses and spin magnitudes and orientations. The solutions are written in a moving reference frame, with the orbital angular momentum and binary radial directions aligned along two of the axes. The resummed solutions show improved accuracy compared to adiabatic solutions while also being an order of magnitude faster computationally compared to numerical integration methods.

Spin-orbital order in LaMnO3 : d−p model study

Using the multiband $d-p$ model and unrestricted Hartree-Fock approximation we investigate the electronic structure and spin-orbital order in three-dimensional MnO$_3$ lattice such as realized in LaMnO$_3$. The orbital order is induced and stabilized by particular checkerboard pattern of oxygen distortions arising from the Jahn-Teller effect in the presence of strong Coulomb interactions on $e_g$ orbitals of Mn ions. We show that the spin-orbital order can be modeled using a simple \textit{Ansatz} for local crystal fields alternating between two sublattices on Mn ions, which have non-equivalent neighboring oxygen distortions in $ab$ planes. The simple and computationally very inexpensive $d-p$ model reproduces correctly nontrivial spin-orbital order observed in undoped LaMnO$_3$. Orbital order is very robust and is reduced by $\sim 3$ \% for large self-doping in the metallic regime.

Heavy fermion materials and physics

As typical examples of strongly correlated electron systems, heavy fermion materials exhibit diverse quantum ground states such as antiferromagnetic order, ferromagnetic order, non-Fermi-liquid phases, unconventional superconductivity, quantum spin liquids, orbital order and topological order. In contrast to other strongly correlated electron systems, heavy fermion systems have relatively small characteristic energy scales, which allows different quantum states to be tuned continuously by using external parameters such as pressure, magnetic field and chemical doping. Heavy fermion materials thus serve as ideal systems for studying quantum phase transitions, superconductivity and their interplay. In this review, we briefly introduce the history of the field of heavy fermions and the current status both in China and in other countries. The properties of several representative heavy fermion systems are summarized, and some frontier scientific issues in this field are discussed, in particular, concerning heavy fermion superconductors, quantum phase transitions and exotic topological states in strongly correlated electron systems.

DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites

With the aim to provide a general protocol to interpret electron paramagnetic resonance (EPR) spectra of paramagnetic copper(II) coordination compounds, density functional theory (DFT) calculations of spin Hamiltonian parameters g and A for fourteen Cu(II) complexes with different charges, donor sets, and geometry were carried out using ORCA software. The performance of eleven functionals was tested, and on the basis of the mean absolute percent deviation (MAPD) and standard deviation (SD), the ranking of the functionals for Az is: B3LYP > B3PW91 ~ B3P86 > PBE0 > CAM-B3LYP > TPSSh > BH and HLYP > B2PLYP > MPW1PW91 > ω-B97x-D >> M06; and for gz is: PBE0 > BH and HLYP > B2PLYP > ω-B97x-D > B3PW91~B3LYP~B3P86 > CAM-B3LYP > TPSSh~MPW1PW91 >> M06. With B3LYP the MAPD with respect to A z exp t l is 8.6% with a SD of 4.2%, while with PBE0 the MAPD with respect to g z exp t l is 2.9% with a SD of 1.1%. The results of the validation confirm the fundamental role of the second order spin-orbit contribution to Az. The computational procedure was applied to predict the values of gz and Az of the adducts formed by Cu(II) with albumin and two fragments of prion protein, 106–126 and 180–193.

Theory of photoinduced ultrafast switching to a spin-orbital ordered hidden phase

Photo-induced hidden phases are often observed in materials with intertwined orders. Understanding the formation of these non-thermal phases is challenging and requires a resolution of the cooperative interplay between different orders on the ultra-short timescale. In this work, we demonstrate that non-equilibrium photo-excitations can induce a state with spin-orbital orders entirely different from the equilibrium state in the three-quarter-filled two-band Hubbard model. We identify a general mechanism governing the transition to the hidden state, which relies on a non-thermal partial melting of the intertwined orders mediated by photoinduced charge excitations in the presence of strong spin-orbital exchange interactions. Our study theoretically confirms the crucial role played by orbital degrees of freedom in the light-induced dynamics of strongly correlated materials and it shows that the switching to hidden states can be controlled already on the fs timescale of the electron dynamics.

Spin canting and orbital order in spinel vanadate thin films

We report on the epitaxial film growth and characterization of CoV$_2$O$_4$, a near-itinerant spinel vanadate, grown on (001) SrTiO$_3$. The symmetry lowering of the unit cell from cubic in the bulk to orthorhombic in the films results in dramatic differences in the magnetic anisotropy compared to bulk, as determined from structural and magnetic characterization. Bulk cubic CoV$_2$O$_4$ has been found to defy predictions by showing orbital degeneracy seemingly lasting to very low temperatures, with only small anomalies in magnetization and neutron experiments signaling a possible spin/orbital glass transition at T = 90 K. In epitaxial thin films presented in this paper, structurally tuning the CoV$_2$O$_4$ away from cubic symmetry leads to a completely different low temperature non-collinear ground state. Via magnetization and neutron scattering measurements we show that the 90 K transition is associated with a major spin reorientation away from the ferrimagnetic easy axis [001] to the [110] direction. Furthermore, the V-spins cant away from this direction with extracted perpendicular moments providing evidence of a larger canting angle compared to bulk. This result indicates that compressive strain pushes the system deeper into the insulating state, i.e., away from the localized - itinerant crossover regime.