Quantum magnets with spin $J=2$, which arise in spin-orbit coupled Mott insulators, can potentially display multipolar orders. We carry out an exact diagonalization study of a simple octahedral crystal field Hamiltonian for two electrons, incorporating spin-orbit coupling (SOC) and interactions, finding that either explicitly including the $e_g$ orbitals, or going beyond the rotationally invariant Coulomb interaction within the $t_{2g}$ sector, causes a degeneracy breaking of the $J\!=\!2$ level degeneracy. This can lead to a low-lying non-Kramers doublet carrying quadrupolar and octupolar moments and an excited triplet which supports magnetic dipole moments, bolstering our previous phenomenological proposal for the stabilization of ferro-octupolar order in heavy transition metal oxides. We show that the spontaneous time-reversal symmetry breaking due to ferro-octupolar ordering within the non-Kramers doublet leads to electronic orbital loop currents. The resulting internal magnetic fields can potentially explain the small fields inferred from muon-spin relaxation ($μ$SR) experiments on cubic $5d^2$ osmate double perovskites Ba$_2$ZnOsO$_6$, Ba$_2$CaOsO$_6$, and Ba$_2$MgOsO$_6$, which were previously attributed to weak dipolar magnetism. We make further predictions for oxygen NMR experiments on these materials. We also study the reversed level scheme, where the $J\!=\!2$ multiplet splits into a low-lying magnetic triplet and excited non-Kramers doublet, presenting single-ion results for the magnetic susceptibility in this case, and pointing out its possible relevance for the rhenate Ba$_2$YReO$_6$. Our work highlights the intimate connection between the physics of heavy transition metal oxides and that of $f$-electron based heavy fermion compounds.
In 5$d^2$ Mott insulators with strong spin-orbit coupling, the lowest pseudospin states form a non-Kramers doublet, which carries quadrupolar and octupolar moments. A family of double perovskites where magnetic ions form a face-centered cubic (fcc) lattice was suggested to unveil an octupolar order offering a rare example in $d$-orbital systems. The proposed order requires a ferromagnetic (FM) octupolar interaction, since the antiferromagnetic (AFM) Ising model is highly frustrated on the fcc lattice. A microscopic model was recently derived for various lattices: for an edge-sharing octahedra …
Exotic high-rank multipolar order parameters have been found to be unexpectedly active in more and more correlated materials in recent years. Such multipoles are usually dubbed as "Hidden Orders" since they are insensitive to common experimental probes. Theoretically, it is also difficult to predict multipolar orders via \textit{ab initio} calculations in real materials. Here, we present an efficient method to predict possible multipoles in materials based on linear response theory under random phase approximation. Using this method, we successfully predict two pure meta-stable magnetic octupo…
Motivated by the recent development in strong spin-orbit-coupled materials, we consider the dipole-octupole doublets on the triangular lattice. We propose the most general interaction between these unusual local moments. Due to the spin-orbit entanglement and the special form of its wavefunction, the dipole-octupole doublet has a rather peculiar property under the lattice symmetry operation. As a result, the interaction is highly anisotropic in the pseudospin space, but remarkably, is uniform spatially. We analyze the ground state properties of this generic model and emphasize the hidden multi…
Broken symmetries in solids involving higher order multipolar degrees of freedom are historically referred to as "hidden orders" due to the formidable task of detecting them with conventional probes. Examples of such hidden orders include spin-nematic order in quantum magnets, and quadrupolar or higher multipolar orders in various correlated quantum materials. In this work, we theoretically propose that the study of magnetostriction provides a powerful and novel tool to directly detect higher-order multipolar symmetry breaking $-$ such as the elusive octupolar order $-$ by examining its scalin…
A series of Pr(TM)$_2$X$_{20}$ (with TM=Ti,V,Rh,Ir and X=Al,Zn) Kondo materials, containing non-Kramers Pr$^{3+}$ $4f^2$ moments on a diamond lattice, have been shown to exhibit intertwined orders such as quadrupolar order and superconductivity. Motivated by these experiments, we propose and study a Landau theory of multipolar order to capture the phase diagram and its field dependence. In zero magnetic field, we show that different quadrupolar states, or the coexistence of quadrupolar and octupolar orderings, may lead to ground states with multiple broken symmetries. Upon heating, such states…
Notable non-Fermi liquid and quantum critical behaviors are observed in rare-earth metallic systems with non-Kramers local moments supporting a number of different multipolar moments. A prominent example is $\text{Pr(Ti,V)}_{2}\text{Al}_{20}$, where the non-Kramers doublet of the $\text{Pr}^{3+}$ ion allows quadrupolar and octupolar moments, but lacks a dipolar moment. Previous theoretical studies show that a single impurity Kondo problem with such an unusual local moment leads to novel non-Fermi liquid states. In this work, we investigate possible quantum critical behaviors arising from the c…
Hidden Magnetic Octupolar Order driven by Spin-Orbit coupling in KFeF$_3$
University of Warwick（华威大学）；Durham University（杜伦大学）；University of Edinburgh（爱丁堡大学）；European Synchrotron Radiation Facility（欧洲同步辐射装置）；Institut Laue-Langevin（朗之万研究所）
When the ground state of a localized ion is a non-Kramers doublet, such localized ions may carry multipolar moments. For example, Pr$^{3+}$ ions in a cubic environment would possess quadrupolar and octupolar, but no magnetic dipole, moments. When such multipolar moments are placed in a metallic host, unusual interactions between these local moments and conduction electrons arise, in contrast to the familiar magnetic dipole interactions in the classic Kondo problem. In this work, we consider the interaction between a single quadrupolar-octupolar local moment and conduction electrons with $p$-or…
The invariant form of the hyperfine interaction between multipolar moments and the nuclear spin is derived, and applied to discuss possibilities to identify the antiferro-octupolar (AFO) moments by NMR experiments. The ordered phase of NpO$_{2}$ and the phase IV of Ce$_{1-x}$La$_{x}$B$_{6}$ are studied in detail. Recent $^{17}$O NMR for polycrystalline samples of NpO$_{2}$ are discussed theoretically from our formulation. The observed feature of the splitting of $^{17}$O NMR spectrum into a sharp line and a broad line, their intensity ratio, and the magnetic field dependence of the shift and o…
Polaron-driven switching of octupolar order in doped 5d$^2$ double perovskite
University of Vienna（维也纳大学）；CPHT, CNRS, École polytechnique, Institut Polytechnique de Paris（巴黎综合理工学院）；Collège de France, Université PSL（法兰西公学院）；Department of Physics and Astronomy ”Augusto Righi”, Alma Mater Studiorum - Università di Bologna（博洛尼亚大学）
d- and f-shells support a large number of local degrees of freedom: dipoles, quadrupoles, octupoles, hexadecapoles, etc. Usually, the ordering of any multipole component leaves the system sufficiently symmetrical to allow a second symmetry breaking transition. Assuming that a second continuous phase transition occurs, we classify the possibilities. We construct the symmetry group of the first ordered phase, and then re-classify the order parameters in the new symmetry. While this is straightforward for dipole or quadrupole order, it is less familiar for octupole order. We give a group theoreti…
Motivated by experimental and theoretical interest in realizing multipolar orders in $d$-orbital materials, we discuss the quantum magnetism of $J\!=\!2$ ions which can be realized in spin-orbit coupled oxides with $5d^2$ transition metal ions. Based on the crystal field environment, we argue for a splitting of the $J\!=\!2$ multiplet, leading to a low lying non-Kramers doublet which hosts quadrupolar and octupolar moments. We discuss a microscopic mechanism whereby the combined perturbative effects of orbital repulsion and antiferromagnetic Heisenberg spin interactions leads to ferro-octupola…
We propose a new type of Dzyaloshinskii-Moriya (DM) interactions which act on high-rank multipolar moments such as quadrupolar and octupolar moments. Here we consider 5d1 systems with broken spatial inversion symmetry, where the interplay of electron correlation, the spin-orbit coupling, and inversion symmetry breaking plays a crucial role. Using a numerical diagonalization on a two-site multiorbital Hubbard model, we reveal that anti-symmetric products of multipole operators have finite expectation values, indicating the existence of DM interactions for multipoles. We also find that the spin-…
We report time-of-flight neutron spectroscopic and diffraction studies of the 5$d^2$ cubic double pervoskite magnets, Ba$_2$MOsO$_6$ ($M$ = Zn, Mg, Ca). These cubic materials are all described by antiferromagnetically-coupled 5$d^2$ Os$^{6+}$ ions decorating a face-centred cubic (FCC) lattice. They all exhibit thermodynamic anomalies consistent with phase transitions at a temperature $T^*$, and exhibit a gapped magnetic excitation spectrum with spectral weight concentrated at wavevectors typical of type I antiferromagnetic orders. While muon spin resonance experiments show clear evidence for t…
In the spin-1/2 frustrated chain with nearest-neighbor ferromagnetic exchange J1 and next-nearest-neighbor antiferromagnetic exchange J2 under magnetic field, magnetic multipolar-liquid (quadrupolar, octupolar, and hexadecapolar) phases are widely expanded from the saturation down to a low-field regime. Recently, we have clarified characteristic temperature and field dependence of the NMR relaxation rate 1/T_1 in the quadrupolar phase. In this paper, we examine those of 1/T_1 in the octupolar phase combining field theoretical method with numerical data. The relevance of the results to quasi on…
Owing to comparably strong spin-orbit coupling and Hubbard interaction, iridium based 227 pyrochlore oxides harbor a rich confluence of competing magnetic orders and emergent multipolar Weyl quasiparticles. Here we show that this family of materials is predominantly susceptible toward the nucleation of electronic noncoplanar all-in all-out (AIAO) and three-in one-out (3I1O) orders, respectively transforming under the singlet $A_{2u}$ and triplet $T_{1u}$ representations, supporting octupolar and dipolar Weyl fermions, and favored by strong on-site Hubbard and nearest-neighbor ferromagnetic int…
Multipolar interactions are derived in the orbitally degenerate Anderson lattice with a spherical Fermi surface and one conduction electron per unit cell of the simple cubic lattice. As the crystalline-electric-field (CEF) ground state of $f^1$ configuration, the four-fold degenerate $Γ_8$ is mainly studied. Intersite interactions up to a sufficiently distant pair are Fourier transformed to the wavenumber space. For the $Γ_8$ case, quadrupolar and octupolar interactions favor the staggered order with $\mib{q} = (1/2,1/2,1/2)$, while the dipolar interaction favors an incommensurate magnetic str…
The origin of non-collinear magnetism under quadrupolar ordering is investigated with CeB6 taken as a target system. The mode-mixing effect among 15 multipoles is analyzed based on the Ginzburg-Landau free energy. Then the lower magnetic transition temperature and the order parameters are derived within the mean-field approximation. In the presence of pseudo-dipole-type interactions for the next-nearest neighbors, the observed pattern of non-collinear ordering is indeed stabilized for certain set of interaction parameters. The stability of the phase III' in the magnetic field is also explained…
Discovery of novel spin-orbital entangled quantum ground states paves an important avenue for controllable quantum materials via unique couplings to the lattice and other external perturbations. In this work, motivated by recent experiments on cubic heavy fermion materials with multipolar local moments, we theoretically investigate strongly-interacting spin-orbital entangled quantum ground states in multipolar quantum impurity systems. Here itinerant electrons are interacting with the local moments carrying quadrupolar and octupolar moments, in contrast to the conventional Kondo problem with d…
We present the phase diagram of the frustrated ferromagnetic S=1/2 Heisenberg J_1-J_2 chain in a magnetic field, obtained by large scale exact diagonalizations and density matrix renormalization group simulations. A vector chirally ordered state, metamagnetic behavior and a sequence of spin-multipolar Luttinger liquid phases up to hexadecupolar kind are found. We provide numerical evidence for a locking mechanism, which can drive spiral states towards spin-multipolar phases, such as quadrupolar or octupolar phases. Our results also shed light on previously discovered spin-multipolar phases in …
Recent experiments have discovered multipolar orders in a variety of $d$-orbital Mott insulators. Motivated by uncovering the exchange interactions which underlie octupolar order proposed in the osmate double perovskites, we study a two-site model using exact diagonalization on a five-orbital Hamiltonian, incorporating spin-orbit coupling (SOC) and interactions, and including both intra-orbital and inter-orbital hopping. Using an exact Schrieffer-Wolff transformation, we then extract an effective pseudospin Hamiltonian for the non-Kramers doublets, uncovering dominant ferrooctupolar coupling d…
The multipolar Kondo problem, wherein the quantum impurity carries higher-rank multipolar moments, has seen recent theoretical and experimental interest due to proposals of novel non-Fermi liquid states and the availability of a variety of material platforms. The multipolar nature of local moments, in conjunction with constraining crystal field symmetries, leads to a vast array of possible interactions and resulting non-Fermi liquid ground states. Previous works on Kondo physics have typically focussed on impurities that have two degenerate internal states. In this work, inspired by recent exp…
Multipolar magnetic phases in correlated insulators represent a great challenge for Density Functional Theory (DFT) due to the coexistence of intermingled interactions, typically spin-orbit coupling, crystal field and complex non-collinear and high-rank inter-site exchange, creating a complected configurational space with multiple minima. Though the +U correction to DFT allows, in principle, the modelling of such magnetic ground states, its results strongly depend on the initially symmetry breaking, constraining the nature of order parameter in the converged DFT+U solution. As a rule, DFT+U ca…
To explore the formation of noncollinear magnetic configurations in materials with strongly correlated electrons, we derive a noncollinear LSDA+$U$ model involving only one parameter $U$, as opposed to the difference between the Hubbard and Stoner parameters $U-J$. Computing $U$ in the constrained random phase approximation, we investigate noncollinear magnetism of uranium dioxide UO$_2$ and find that the spin-orbit coupling (SOC) stabilizes the 3$\textbf{k}$ ordered magnetic ground state. The estimated SOC strength in UO$_2$ is as large as 0.73 eV per uranium atom, making spin and orbital deg…
We investigate with a microscopic model anharmonic K-cation oscillation observed by neutron experiments in beta-pyrochlore superconductor KOs2O6, which also shows a mysterious first-order structural transition at Tp=7.5 K. We have identified a set of microscopic model parameters that successfully reproduce the observed temperature dependence and the superconducting transition temperature. Considering changes in the parameters at Tp, we can explain puzzling experimental results about electron-phonon coupling and neutron data. Our analysis demonstrates that the first-order transition is multipol…
The magnetic properties of the pyrochlore iridate material Eu$_2$Ir$_2$O$_7$ (5$d^5$) have been studied based on the first principle calculations, where the crystal field splitting $Δ$, spin-orbit coupling (SOC) $λ$ and Coulomb interaction $U$ within Ir 5$d$ orbitals are all playing significant roles. The ground state phase diagram has been obtained with respect to the strength of SOC and Coulomb interaction $U$, where a stable anti-ferromagnetic ground state with all-in/all-out (AIAO) spin structure has been found. Besides, another anti-ferromagnetic states with close energy to AIAO have also…
We review the cubic rare-earth boride series which displays diverse electronic states like localized 4f electron multiplets split by the crystal electric field (CEF), itinerant heavy-fermion quasiparticle bands of the Kondo lattice as well as gapped Kondo insulator or mixed-valent semiconductor states. Fairly exotic states may appear due to the 'hidden' order of multipoles carried by degenerate CEF multiplets, in addition to magnetic order present in many RB6 (R = rare earth) compounds. Most prominent are CeB6 and its La-diluted alloys which exhibit antiferro-quadrupolar and octupolar ordering…
Multipolar magnetism is an emerging field of quantum materials research. The building blocks of multipolar phenomena are magnetic ions with a non-Kramers doublet, where the orbital and spin degrees of freedom are inextricably intertwined, leading to unusual spin-orbital entangled states. The detection of such subtle forms of matter has, however, been difficult due to a limited number of appropriate experimental tools. In this work, motivated by a recent magnetostriction experiment on Pr$_2$Zr$_2$O$_7$, we theoretically investigate how multipolar quantum spin ice, an elusive three dimensional q…
In contrast to magnetic order formed by electrons' dipolar moments, ordering phenomena associated with higher-order multipoles (quadrupoles, octupoles, etc.) are more difficult to characterize because of the limited choice of experimental probes that can distinguish different multipolar moments. The heavy-fermion compound CeB6 and its La-diluted alloys are among the best-studied realizations of the long-range-ordered multipolar phases, often referred to as "hidden order". Previously the hidden order in phase II was identified as primary antiferroquadrupolar (AFQ) and field-induced octupolar (A…
We illustrate how the tensorial kernel support vector machine (TK-SVM) can probe the hidden multipolar orders and emergent local constraint in the classical kagome Heisenberg antiferromagnet. We show that TK-SVM learns the finite-temperature phase diagram in an unsupervised way. Moreover, in virtue of its strong interpretability, it identifies the tensorial quadrupolar and octupolar orders, which define a biaxial $D_{3h}$ spin nematic, and the local constraint that underlies the selection of coplanar states. We then discuss the disorder hierarchy of the phases, which can be inferred from both …
Study of the combined effects of strong electronic correlations with spin-orbit coupling (SOC) represents a central issue in quantum materials research. Predicting emergent properties represents a huge theoretical problem since the presence of SOC implies that the spin is not a good quantum number. Existing theories propose the emergence of a multitude of exotic quantum phases, distinguishable by either local point symmetry breaking or local spin expectation values, even in materials with simple cubic crystal structure such as Ba$_2$NaOsO$_6$. Experimental tests of such theories by local probe…
Experiments in the recently discovered vanadium-based kagome metals have suggested that their charge-ordered state displays not only bond distortions, characteristic of a ``real" charge density-wave (rCDW), but also time-reversal symmetry-breaking, typical of loop currents described by an ``imaginary" charge density-wave (iCDW). Here, we combine density-functional theory, group-theory, and phenomenological modeling to investigate the complex charge-ordered states that arise from interactions between the low-energy van Hove singularities present in the electronic structure of $A$V$_3$Sb$_5$. We…
We have carried out a detailed first-principles study of a d$^{4.5}$ quaternary iridate Ba$_3$YIr$_2$O$_9$ both in its 6H-perovskite-type ambient pressure (AP) phase and also for the high pressure (HP) cubic phase. Our analysis reveals that the AP phase belongs to the intermediate spin-orbit coupling (SOC) regime. This is further supported by the identification of the spin moment as the primary order parameter (POP) obtained from a magnetic multipolar analysis. The large $t_{2g}$ band width renormalizes the strength of SOC and the Ir intersite exchange interaction dominates resulting in long r…
In insulating lanthanides, unquenched orbital momentum and weak crystal-field (CF) splitting of the atomic $J$ multiplet at lanthanide ions result in a highly ranked (multipolar) exchange interaction between them and a complex low-temperature magnetic order not fully uncovered by experiment. Explicitly correlated {\it ab initio } methods proved to be highly efficient for an accurate description of CF multiplets and magnetism of individual lanthanide ions in such materials. Here we extend this {\it ab initio } methodology and develop a first-principles microscopic theory of multipolar exchange …
Multipolar Piezoelectricity and Anisotropic Surface Transport in Alterelectrics
University of Amsterdam（阿姆斯特丹大学）；Cavendish Laboratory, University of Cambridge（剑桥大学卡文迪许实验室）；Institute for Theoretical Solid State Physics, IFW Dresden（德累斯顿IFW研究所理论固体物理研究所）；Würzburg-Dresden Cluster of Excellence ctd.qmat（维尔茨堡-德累斯顿卓越集群ctd.qmat）；Institute for Theoretical Physics, TU Dresden（德累斯顿工业大学理论物理研究所）
Neutron scattering is a powerful tool to study magnetic structures and dynamics, benefiting from a precisely established theoretical framework. The neutron dipole moment interacts with electrons in materials via their magnetic field, which can have spin and orbital origins. Yet in most experimentally studied cases the individual degrees of freedom are well described within the dipole approximation, sometimes accompanied by further terms of a multipolar expansion that usually act as minor corrections to the dipole form factor. Here we report a unique example of neutrons diffracted mainly by mag…
Landau Theory for Non-relativistic Magnetism Beyond Altermagnetism
University of California, Irvine（加州大学欧文分校）；Laboratoire Léon Brillouin, CEA, CNRS, Université Paris-Saclay（巴黎-萨克雷大学法国国家科学研究中心法国原子能委员会莱昂·布里渊实验室）；University of Windsor（温莎大学）
Non-magnetic ground state in A$_2$WCl$_6$ (A = Cs, Rb, K): A face-centered cubic system of spin-orbit-entangled $J$ = 2 states
Max Planck Institute for Solid State Research（马克斯·普朗克固相研究所）；Institute for Functional Matter and Quantum Technologies, University of Stuttgart（斯图加特大学功能物质与量子技术研究所）；National Institute for Materials Science（国立材料研究所）；Synchrotron Radiation Research Center, National Institutes for Quantum Science and Technology（量子科学技术研究机构同步辐射研究中心）；Graduate School of Engineering and Science, Shibaura Institute of Technology（芝浦工业大学理工学研究科）；Nuclear Structure Research Group, RIKEN Nishina Center for Accelerator-Based Science（RIKEN仁科加速器科学中心核结构研究组）；ISIS Neutron and Muon Source, STFC Rutherford Appleton Laboratory（STFC卢瑟福阿普尔顿实验室ISIS中子和μ子源）；Department of Physics, University of Tokyo（东京大学物理学系）
As a simple cubic system with only one f electron per cerium ion, CeB6 is of model character to investigate the interplay of orbital phenomena with magnetism. It is also a textbook example of a compound that exhibits magnetically hidden order -- a low-temperature magnetic phase with ordered quadrupolar moments. It is difficult to identify the symmetry of such hidden-order states in common x-ray or neutron scattering experiments, as there is no signal in zero field, however alternative techniques like neutron diffraction in external field, resonant x-ray scattering, or ultrasonic investigations…
