Quadrupolar spin liquid, octupolar Kondo coupling and odd-frequency superconductivity in an exactly solvable model
Carlene S. de Farias, Vanuildo S. de Carvalho, Eduardo Miranda, Rodrigo G. Pereira
备注：
16 pages, 8 figures. We corrected the statement about the number of edge states in the chiral phase of the quadrupolar spin liquid. We also added the appendix B
We propose an exactly solvable model for $j_{\text{eff}}=\frac32$ local moments on the honeycomb lattice. Our construction is guided by a symmetry analysis and by the requirement of an exact solution in terms of a Majorana fermion representation for multipole operators. The main interaction in the model can be interpreted as a bond-dependent quadrupole-quadrupole interaction. When time reversal symmetry is explicitly broken, we obtain a gapped spin liquid with a single chiral Majorana edge mode. We also investigate another solvable model in which the time-reversal-invariant spin liquid is coupled to conduction electrons in a superconductor. In the presence of a Kondo-like coupling that involves the octupole moment of the localized spins, the itinerant electrons hybridize with the emergent Majorana fermions in the spin liquid. This leads to spontaneous time reversal symmetry breaking and generates odd-frequency pairing. Our results suggest that $j_{\text{eff}}=\frac32$ systems with strong quadrupole-quadrupole interactions may provide a route towards non-Abelian quantum spin liquids and unconventional superconductivity.
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…
We show how a gapless spin liquid with hidden octupolar order arises in an applied magnetic field, in a model applicable to thin films of 3He with competing ferromagnetic and antiferromagnetic (cyclic) exchange interactions. Evidence is also presented for nematic -- i.e., quadrupolar -- correlations bordering on ferromagnetism in the absence of a magnetic field.
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…
Recent experiments point to a variety of intermetallic systems which exhibit exotic quadrupolar orders driven by the Kondo coupling between conduction electrons and localized quadrupolar degrees of freedom. Using a Luttinger k.p Hamiltonian for the conduction electrons, we study the impact of such quadrupolar order on their energies and wave functions. We discover that such quadrupolar orders can induce a nontrivial Berry curvature for the conduction electron bands, leading to a nonvanishing optical gyrotropic effect. We estimate the magnitude of the gyrotropic response in a candidate quadrupo…
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 …
The cubic compound PrTi$_2$Al$_{20}$ is a quadrupolar Kondo lattice system that exhibits quadrupolar ordering due to the non-Kramers $Γ_3$ ground doublet and has strong hybridization between $4f$ and conduction electrons. Our study using high-purity single crystal reveals that PrTi$_2$Al$_{20}$ exhibits type-II superconductivity at $T_{\rm c} = 200$ mK in the nonmagnetic ferroquadrupolar state. The superconducting critical temperature and field phase diagram suggests moderately enhanced effective mass of $m^*/m_0 \sim 16$.
We performed ultrasonic measurement on the rare-earth intermetallic compound PrInAg_2 to examine the quadrupolar Kondo effect associated with the non-Kramers Gamma_3 doublet ground state. The characteristic softening of the elastic constant (c_{11}-c_{12})/2 below 10 K in PrInAg_2 is attributed to a Curie term in quadrupolar susceptibility for the quadrupole O_2^2=J_x^2-J_y^2 of the stable Gamma_3 ground state. (c_{11}-c_{12})/2 turns to a slight increase with the -lnT dependence below 0.1 K, which suggests the quenching of the quadrupolar moment in the quadrupolar Kondo state. Under applied m…
Acoustic signatures of the single-site quadrupolar Kondo effect in Y$_{0.966}$Pr$_{0.034}$Ir$_2$Zn$_{20}$ are presented. The elastic constant ($C_{11}-C_{12}$)/2, corresponding to the $Γ_3$(E)-symmetry electric-quadrupolar response, reveals a logarithmic temperature dependence of the quadrupolar susceptibility in the low-magnetic-field region below $\sim$0.3 K. Furthermore, the Curie-type divergence of the elastic constant down to $\sim$1 K indicates that the Pr ions in this diluted system have a non-Kramers ground-state doublet. These observations evidence the single-site quadrupolar Kondo ef…
We report on the low-temperature thermal expansion and magnetostriction of the single-impurity quadrupolar Kondo candidate Y$_{1-x}$Pr$_{x}$Ir$_2$Zn$_{20}$. In the dilute limit, we find a quadrupolar strain that possesses a singular dependence on temperature $T$, $\varepsilon_{\mathrm{u}} \sim H^2 \log 1/T$, for a small but finite magnetic field $H$. Together with the previously reported anomalous specific heat $C$, this implies a quadrupolar Grüneisen ratio $Γ_u = \partial_T \varepsilon_{\mathrm{u}}/C \sim H^2/(T^2 \log 1/T)$ whose divergence for finite $H$ is consistent with the scenario of …
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…
Heavy fermion metals hosting multipolar local moments set a new stage for exploring exotic spin-orbital entangled quantum phases. In such systems, the quadrupolar Kondo effect serves as the key ingredient in the orbital-driven non-Fermi liquid (NFL) behavior and quantum critical phenomena. The cubic heavy fermion superconductor Pr$Tr_2$Al$_{20}$ ($Tr$: Ti, V) is a prime candidate for realizing the quadrupolar Kondo lattice. Here, we present a systematic study of the NFL phenomena in PrV$_2$Al$_{20}$ based on magnetoresistance (MR), magnetic susceptibility and specific heat measurements. Upon e…
We theoretically investigate the origin of the resonant x-ray scattering (RXS) signal near the Ce $L_{III}$ absorption edge in the quadrupolar ordering phase of CeB$_6$, considering the intersite interaction between the $Γ_8$ states in the initial state. The anisotropic charge distribution of the $4f$ states modulates the $5d$ states through the intra-atomic Coulomb interaction and thereby generates a large RXS superlattice intensity. The temperature and magnetic field dependence indicates that the induced dipolar and octupolar orders have little influence on the RXS spectra, in good agreement…
We have measured the specific heat of PrV$_2$Al$_{20}$ at very low temperatures, using high quality single crystals with the residual resistivity ratio ~ 20. The high-quality single crystals exhibit clear double transitions at $T_{\rm Q} =$ 0.75 K and $T^* =$ 0.65 K. These transitions are clearer and shift to higher temperature in higher quality single crystals. Besides, there was no hysteresis in those transitions in warming and cooling process of the heat capacity measurements. In the ordered state below $T^*$, the specific heat shows a $T^4$ dependence, indicating the gapless mode associate…
Our single crystal study reveals that PrTr2Al20 (Tr = Ti and V) provides the first examples of a cubic Γ3 nonmagnetic ground doublet system that shows the Kondo effect including a -ln T dependent resistivity. The Γ3 quadrupolar moments in PrV2Al20 induce anomalous metallic behavior through hybridization with conduction electrons, such as T^{1/2} dependent resistivity and susceptibility below ~ 20 K down to its ordering temperature T_O = 0.6 K. In PrTi2Al20, however, quadrupoles are well-localized and exhibit an order at T_O = 2.0 K. Stronger Kondo coupling in PrV2Al20 than in PrTi2Al20 suppres…
In non-Kramers Kondo systems with a quadrupolar degrees of freedom, an ordinary magnetic Kondo effect can compete with the quadrupolar Kondo effect. We discuss such competition keeping Pr$T_{2}$Zn$_{20}$ ($T$=Ir, Rh) and Pr$T_{2}$Al$_{20}$ ($T$=V, Ti) in mind, where the $Γ_{3}$ non-Kramers crystalline-electric-field (CEF) doublet ground state is realized in Pr$^{3+}$ ion with $(4f)^{2}$ configuration under cubic symmetry. The quadrupolar Kondo effect can be described by the two-channel Kondo model, which leads to the local non-Fermi-liquid (NFL) ground state, while the magnetic Kondo effect fa…
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…
We have measured the electric resistivity, magnetoresistance, magnetic susceptibility and magnetization of the new Kondo-lattice compound Ce3Pd4Ge4. The electrical resistivity exhibits a rapid drop at temperatures below 6 K, while the magnetic susceptibility does not show any corresponding anomaly at that temperature. This phenomenon is similar to that of Ce3Pd20Ge6 which shows quadrupolar interation. We suggest that there is the possibility of quadrupolar interaction in the orthorhombic 4f-electron system Ce3Pd4Ge4. In addition, it is realized that the spin-dependent scattering effect is resp…
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 mom…
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…
We investigate the mixed-valent regime of a two-configuration Anderson impurity model for uranium ions, with separate quadrupolar and magnetic doublets. With a new Monte Carlo approach and the non-crossing approximation we find: (i) A non-Fermi-liquid fixed point with two-channel Kondo model critical behavior; (ii) Distinct energy scales for screening the low-lying and excited doublets; (iii) A semi-quantitative explanation of magnetic-susceptibility data for U$_{1-x}$Th$_x$Be$_{13}$ assuming 60-70% quadrupolar doublet ground-state weight, supporting the quadrupolar-Kondo interpretation.
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…
We study a realistic Kondo model for crystal field quartet ground states having magnetic and non-magnetic (quadrupolar) exchange couplings with conduction electrons, using the numerical renormalization group method. We focus on a local effect dependent on singlet excited states coupled to the quartet, which reduces the non-magnetic coupling significantly and drives non-Fermi liquid behavior observed in the calculated quadrupolar susceptibility. A crossover from the non-Fermi liquid state to the Fermi liquid state is characterized by a small energy scale very sensitive to the non-magnetic coupl…
A magnetic Bragg reflection corresponding to the wave vector k13 = (2pi/a)[1/2,1/2,1/2] of the antiferro-quadrupolar ordering is found in CeB6 in zero magnetic field below the Neel temperature TN. Its intensity is two orders of magnitude weaker than those due to the basic magnetic structure [O. Zaharko et al., Phys. Rev. B 68, 214401 (2003)]. The peak has a width of the other Bragg reflections below TN, but widens abruptly at T = TN with simultaneous increase of intensity. Correlation length just above TN is of the order of 70 A. The peak intensity decreases to zero at T = 7 K with no visible …
We have studied the low-temperature properties of Pr$_{x}$La$_{1-x}$Pb$_{3}$ with non-Kramers $Γ_{3}$ quadrupolar moments of the crystal-electric-field ground state, for a wide concentration range of Pr ions. For $x$$\le$0.05, the specific heat $C/T$ increases monotonically below $T$=1.5 K, which can be scaled with a characteristic temperature $T^{*}$ defined at each concentration $x$. The electrical resistivity $ρ$$(T)$ in the corresponding temperature region shows a marked decrease deviating from a Fermi-liquid behavior $ρ$$(T)$$\propto$$T^{2}$. The Kondo effect arising from the correlation …
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…
Experimental evidence of the magnetic resonance in the antiferro-quadrupole phase of CeB6 is reported. We have shown that below orbital ordering temperature a new magnetic contribution from localized magnetic moments (LMM) emerge and gives rise to observed resonant phenomenon. This behaviour is hardly possible to expect in dense Kondo system, where LMM should vanish al low temperatures rather than emerge. From the other hand, in the quadrupole ordering concept, where magnetism of Ce magnetic ions is solely accounted, is difficult to explain splitting of magnetisation into components having dif…
Among heavy fermion materials, there is a set of rare-earth intermetallics with non-Kramers Pr$^{3+}$ $4f^2$ moments which exhibit a rich phase diagram with intertwined quadrupolar orders, superconductivity, and non-Fermi liquid behavior. However, more subtle broken symmetries such as multipolar orders in these Kondo materials remain poorly studied. Here, we argue that multi-spin interactions between local moments beyond the conventional two-spin exchange must play an important role in Kondo materials near the ordered to heavy Fermi liquid transition. We show that this drives a plethora of pha…
In frustrated magnets when magnetic ordering is suppressed down to low temperature, the formation of a quantum spin liquid becomes a possibility. How such a spin liquid manifests in the presence of conduction electrons is a question with potentially rich physical consequences, particularly when both the localized spins and conduction electrons reside on frustrated lattices. We propose a novel mechanism for symmetry breaking in systems where conduction electrons hybridize with a quantum spin liquid through Kondo couplings. We apply this to the pyrochlore iridate Pr2Ir2O7, which exhibits an anom…
Ultrasonic investigations of the single-site quadrupolar Kondo effect in diluted Pr system Y$_{0.966}$Pr$_{0.034}$Ir$_2$Zn$_{20}$ are reported. The elastic constant $(C_{11}-C_{12})/2$ is measured down to ~40 mK using ultrasound for the dilute system Y$_{0.966}$Pr$_{0.034}$Ir$_2$Zn$_{20}$ and the pure compound YIr$_2$Zn$_{20}$. We found that the elastic constant $(C_{11}-C_{12})/2$ of the Pr-dilute system exhibits a logarithmic temperature dependence below $T_0$ ~0.3 K, where non-Fermi-liquid (NFL) behavior in the specific heat and electrical resistivity is observed. This logarithmic temperatu…
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…
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-…
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…
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）
We examine the RKKY interactions of CeB$_6$ between multipole moments based on the effective Wannier model obtained from the bandstructure calculation including 14 Ce-$f$ orbitals and 60 conduction orbitals of Ce-$d,s$ and B-$p,s$. By using the $f$-$c$ mixing matrix elements of the Wannier model together with the conduction band dispersion, the multipole couplings with the RKKY oscillation are obtained for the active moments in $Γ_{8}$ subspace. Both of the $Γ_{5g}$ quadrupole $O_{xy}$ and the $Γ_{2u}$ octupole $T_{xyz}$ couplings are largely enhanced with $\bm{q}=(π,π,π)$ which naturally expl…
CeRh2As2 has recently been reported to be a rare case of multi-phase unconventional superconductor [S. Khim et al., arXiv:2101.09522] close to a quantum critical point (QCP). Here, we present a comprehensive study of its normal state properties and of the phase (I) below To ~ 0.4 K which preempts superconductivity at Tc = 0.26 K. The 2nd-order phase transition at To presents signatures in specific heat and thermal expansion, but none in magnetization and ac-susceptibility, indicating a non-magnetic origin of phase I. In addition, an upturn of the in-plane resistivity at To points to a gap open…
We have investigated the elastic properties of the Ce-based filled skutterudite antimonides CeRu$_{4}$Sb$_{12}$ and CeOs$_{4}$Sb$_{12}$ by means of ultrasonic measurements. CeRu$_{4}$Sb$_{12}$ shows a slight increase around 130 K in the temperature dependence of the elastic constants $C$$_{11}$, ($C$$_{11}$-$C$$_{12}$)/2 and $C$$_{44}$. No apparent softening toward low temperature due to a quadrupolar response of the 4$f$-electronic ground state of the Ce ion was observed at low temperatures. In contrast CeOs$_{4}$Sb$_{12}$ shows a pronounced elastic softening toward low temperature in the lon…
We construct and analyze a microscopic model for insulating rock salt ordered double perovskites, with the chemical formula A$_2$BB'O$_6$, where the B' atom has a 4d$^1$ or 5d$^1$ electronic configuration and forms a face centered cubic (fcc) lattice. The combination of the triply-degenerate $t_{2g}$ orbital and strong spin-orbit coupling forms local quadruplets with an effective spin moment $j=3/2$. Moreover, due to strongly orbital-dependent exchange, the effective spins have substantial biquadratic and bicubic interactions (fourth and sixth order in the spins, respectively). This leads, at …
Orbital degrees of freedom in condensed matters could play important roles in forming a variety of exotic electronic states by interacting with conduction electrons. In 4f electron systems, because of strong intra-atomic spin-orbit coupling, an orbitally degenerate state inherently carries quadrupolar degrees of freedom. The present work has focussed on a purely quadrupole-active system PrIr2Zn20 showing superconductivity in the presence of an antiferroquadrupole order at TQ = 0.11 K. We observed non-Fermi liquid (NFL) behaviors emerging in the electrical resistivity and the 4f contribution to…
We have investigated the electronic states of CeB$_6$ and have directly calculated the RKKY interaction on the basis of the 74-orbital effective Wannier model which includes 14 Ce-$f$ orbitals and 60 conduction ($c$) orbitals of Ce-$d,s$ and B-$p,s$ derived from the density-functional theory bandstructure calculation. By using not only the $c$-band dispersion but also the $f$-$c$ mixing matrix elements of the Wannier model, the realistic couplings for all 15 active multipole moments in $Γ_8$ quartet subspace are obtained in the wavevector $q$-space and real-space. Both of the $Γ_{5g}$ quadrupo…
