We report comprehensive Raman-scattering measurements on a single crystal of double-perovskite Nd2ZnIrO6 in temperature range of 4-330 K, and spanning a broad spectral range from 20 cm-1 to 5500 cm-1. The paper focuses on lattice vibrations and electronic transitions involving Kramers doublets of the rare-earth Nd3+ ion with local C1 site symmetry. Temperature evolution of these quasi-particle excitations have allowed us to ascertain the intricate coupling between lattice and electronic degrees of freedom in Nd2ZnIrO6. Strong coupling between phonons and crystal-field excitation is observed via renormalization of the self-energy parameter of the phonons i.e. peak frequency and line-width. The phonon frequency shows abrupt hardening and line-width narrowing below ~ 100 K for the majority of the observed first-order phonons. We observed splitting of the lowest Kramers doublets of ground state (4I9/2) multiplets i.e. lifting of the Kramers degeneracy, prominently at low-temperature (below ~ 100 K), attributed to the Nd-Nd/Ir exchange interactions and the intricate coupling with the lattice degrees of freedom. The observed splitting is of the order of ~ 2-3 meV and is consistent with the estimated value. We also observed a large number of high-energy modes, 46 in total, attributed to the intra-configurational transitions between 4f3 levels of Nd3+ coupled to the phonons reflected in their anomalous temperature evolution.
We formulate and study an effective Hamiltonian for low-energy Kramers doublets of $d^1$-ions on a square lattice. We find that the system exhibits a magnetically hidden order in which the expectation values of the local spin and orbital moments both vanish. The order parameter responsible for a time-reversal symmetry breaking has a composite nature and is a spin-orbital analog of a magnetic octupole. We argue that such a hidden order is realized in the layered perovskite Sr$_2$VO$_4$.
We study stability of multiple conducting edge states in a topological insulator against all multi-particle perturbations allowed by the time-reversal symmetry. We model a system as a multi-channel Luttinger liquid, where the number of channels equals the number of Kramers doublets at the edge. We show that in the clean system with N Kramers doublets there always exist relevant perturbations (either of superconducting or charge density wave character) which always open (N-1) gaps. In the charge density wave regime, (N-1) edge states get localised. The single remaining gapless mode describes sl…
We report magnetic properties of a 4f-honeycomb iodide SmI3 made up of edge-shared network of SmI6 octahedra. High temperature magnetic susceptibility indicates Γ7 Kramers doublet ground state of Sm3+ (4f5) ions stabilized by the spin-orbit coupling and octahedral crystal electric field, which interact with Sm-I-Sm bond angle nearly 90 degree. Magnetization measurements down to 0.1 K detected antiferromagnetic correlations and an anomaly in the magnetization curve before saturation without a sign of long-range order. Relevance between SmI3 and the antiferromagnetic Kitaev material proposed in …
We study the multipole interactions between $f^2$ ions with the $Γ_3$ non-Kramers doublet ground state under a cubic crystalline electric field. We construct the $Γ_3$ doublet state of the electrons with the total angular momentum $j=5/2$. By applying the second-order perturbation theory with respect to the intersite hopping, we derive the multipole interactions. We obtain a quadrupole interaction for a simple cubic lattice, an octupole interaction for a bcc lattice, and both quadrupole and octupole interactions for an fcc lattice. We also discuss general tendencies of the multipole interactio…
Cubic Pr-based compounds with $Γ_3$ non-Kramers doublet ground states can realize a novel heavy Fermi liquid with spinorial hybridization ('hastatic' order) that breaks time reversal symmetry. Several Pr-"1-2-20" materials exhibit a suggestive heavy Fermi liquid stabilized in intermediate magnetic fields; these provide key insight into the quadrupolar Kondo lattice. We develop a simple, yet realistic microscopic model of ferrohastatic order, and elaborate its experimental signatures and behavior in field, where it is a good candidate to explain the observed heavy Fermi liquids at intermediate …
We discuss possible competition between magnetic and quadrupole Kondo effects in non-Kramers doublet systems under cubic symmetry. The quadrupole Kondo effect leads to non-Fermi-liquid (NFL) ground state, while the magnetic one favors ordinary Fermi liquid (FL). In terms of the $j$-$j$ coupling scheme, we emphasize that the orbital fluctuation must develop in the vicinity of the NFL-FL boundary. We demonstrate a change of behavior in the f-electron entropy by the Wilson's numerical renormalization-group (NRG) method on the basis of the extended two-channel Kondo exchange model. We present impl…
We investigate antiferro quadrupole orders in systems with non-Kramers doublet ground state with total angular momentum J=4 in T_d point group symmetry. We demonstrate that a pure O_2^2 antiferro quadrupole order is impossible in general crystalline-electric field potential and should be accompanied by ferro O_2^0 quadrupole moment. The temperature and magnetic-field phase diagram is obtained by mean-field approximation of intersite quadrupole interactions and the excitation spectrum is analyzed by "spin"-wave approximations. Gapless excitations emerge at the boader of antiferro O_2^2 quadrupo…
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…
We consider the simplest variant of a Kondo insulator where a doublet of localized $f$-electrons hybridizes with spin-degenerate conduction electrons. We analyse the symmetries of $f$-orbitals involved in the hybridization and point out that the effective four-band model of such systems is adiabatically connected with one that possesses chiral symmetry, which provides further descriptions of clean Kondo insulators. We obtain general conditions for the appearance of topological non-trivial states and discuss implications for rare-earth based compounds. As an example, we derive the full phase di…
Goldstone modes emerge associated with spontaneous breakdown of the continuous symmetry in the two-channel Kondo lattice, which describes strongly correlated f-electron systems with a non-Kramers doublet at each site. This paper derives the spectra of these collective modes by the equation of motion method together with the random phase approximation. The diagonal composite order breaks the SU(2) channel symmetry, and the symmetry-restoring collective mode couples with magnetic field. On the other hand, the off-diagonal or superconducting composite order breaks the gauge symmetry of conduction…
In this study, ultrasonic measurements were performed on a single crystal of cubic PrNi$_2$Cd$_{20}$, down to a temperature of 0.02 K, to investigate the crystalline electric field ground state and search for possible phase transitions at low temperatures. The elastic constant $(C_{11}-C_{12})/2$, which is related to the $Γ_3$-symmetry quadrupolar response, exhibits the Curie-type softening at temperatures below $\sim$30 K, which indicates that the present system has a $Γ_3$ non-Kramers doublet ground state. A leveling-off of the elastic response appears below $\sim$0.1 K toward the lowest tem…
Three dimensional topological superconductors with time reversal symmetry (class DIII) are indexed by an integer $ν$, the number of surface Majorana cones, according to the free fermion classification. The superfluid B phase of He$^3$ realizes the $ν=1$ phase. Recently, it has been argued that this classification is reduced in the presence of interactions to Z$_{16}$. This was argued from the symmetry respecting surface topological orders of these states, which provide a non-perturbative definition of the bulk topological phase. Here, we verify this conclusion by focusing on the even index cas…
Praseodymium-based 1-2-20 cage compounds Pr$T_2X_{20}$ ($T$ is generally Ti, V, Nb, Ru, Rh, Ir; and $X$ is either Al, Zn or Cd) provide yet another platform to study non-trivial electronic states of matter ranging from topological and magnetic orders to unconventional multipolar orders and superconductivity. In this paper, we report measurements of the electronic heat capacity in two Pr-based 1-2-20 materials: PrNi$_2$Cd$_{20}$ and PrPd$_2$Cd$_{20}$. We find that the lowest energy multiplet of the Pr $4f^2$ valence configuration is a $Γ_3$ non-Kramers doublet and the first excited triplet is a…
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…
Localized magnetic moments with crystal-field doublet or pseudo-spin 1/2 may arise in correlated insulators with even number of electrons and strong spin-orbit coupling. Such a non-Kramers pseudo-spin 1/2 is the consequence of crystalline symmetries as opposed to the Kramers doublet arising from time-reversal invariance, and is necessarily a composite of spin and orbital degrees of freedom. We investigate possible spin-orbital liquids with fermionic spinons for such non-Kramers pseudo-spin 1/2 systems on the Kagome lattice. Using the projective symmetry group analysis, we find {\it ten} new ph…
We have investigated the low temperature quadrupolar phenomena of the non-Kramers system PrRh2Zn20 under magnetic fields in the [100] and [110] directions. Our experiments reveal the B-T phase diagram of PrRh2Zn20 involving four electronic states regardless of the field direction, namely, a non-Fermi liquid (NFL) state, an antiferro-quadrupolar (AFQ) ordered state, a novel heavy-fermion (HF) state, and a field-induced singlet (FIS) state. In the wide range of the NFL state, the resistivity can be well scaled by a characteristic temperature, suggesting the realization of the quadrupole Kondo ef…
Motivated by the rapid experimental progress on the spin-orbit-coupled Mott insulators, we propose and study a generic spin model that describes the interaction between the non-Kramers doublets on a triangular lattice and is relevant for triangular lattice rare-earth magnets. We predict that the system supports both pure quadrupolar orders and intertwined multipolar orders in the phase diagram. Besides the multipolar orders, we explore the magnetic excitations to reveal the dynamic properties of the systems. Due to the peculiar properties of the non-Kramers doublets and the selective coupling …
Strongly Quenched Kramers Doublet Magnetism in SmMgAl11O19
Charles University, Faculty of Mathematics and Physics（查理大学数学物理学院）；Adam Mickiewicz University, Faculty of Physics and Astronomy（亚当·密茨凯维奇大学物理与天文学学院）；Institute of Physics of the Czech Academy of Sciences（捷克科学院物理研究所）
The exact diagonalization and the variational cluster approximation (VCA) are used to study the nature of a novel Mott insulator induced by a strong spin-orbit coupling for a two-dimensional three-band Hubbard model consisting of the $t_{2g}$ manifold of $5d$ orbitals. To characterize the ground state, we introduce a local Kramer's doublet which can represent a state with effective angular momentum $J_{\rm eff}=|{\bm S}-{\bm L}|=1/2$ as well as spin $S=1/2$. Our systematic study of the pseudo-spin structure factor defined by the Kramer's doublet shows that the $J_{\rm eff}=1/2$ Mott insulator …
Materials with non-Kramers doublet ground states naturally manifest the two-channel Kondo effect, as the valence fluctuations are from a non-Kramers doublet ground state to an excited Kramers doublet. Here, the development of a heavy Fermi liquid requires a channel symmetry breaking spinorial hybridization that breaks both single and double time-reversal symmetry, and is known as hastatic order. Motivated by cubic Pr-based materials with $Γ_3$ non-Kramers ground state doublets, this paper provides a survey of cubic hastatic order using the simple two-channel Kondo-Heisenberg model. Hastatic or…
A criterion for effective irrelevancy of the spin-orbit coupling in the heavy-fermion superconductivity is discussed on the basis of the impurity Anderson model with two sets of Kramers doublets. Using Wilson's numerical renormalization-group method, we demonstrate a formation of the quasiparticle as well as the renormalization of the rotational symmetry-breaking interaction in the lower Kramers doublet (quasispin) space. A comparison with the quasispin conserving interaction exhibits the effective irrelevancy of the symmetry-breaking interaction for the splitting of two doublets Delta larger …
CeRhSi$_{3}$ is a superconductor under pressure coexisting with a weakly antiferromagnetic phase characterized by a Bragg peak at $\vec{q}_{0}$=($\sim$ 0.2, 0, 0.5) (N. Aso et al. J. Magn. Magn. Mater. 310, 602 (2007)). The compound is also a heavy fermion material with a large specific heat coefficient $γ$=110 mJ $\cdot$ mol$^{-1}$ $\cdot$ K$^{-2}$ and a high Kondo temperature of $T_{K}$=50 K indicative that CeRhSi$_{3}$ is in a strongly Kondo screened state. We apply high resolution neutron spectroscopy to investigate the magnetic fluctuations in the normal phase, at ambient pressures, and a…
Spin reorientation is an important phenomenon of rare-earth perovskites, orthoferrites and orthochromites. In this study, we consider a simple but realistic microscopic theory of the spontaneous spin-reorientation transitions induced by the 4f-3d interaction, more specifically, the interaction of the main Kramers doublet or non-Kramers quasi-doublet of the 4f ion with an effective magnetic field induced by the 3d sublattice. The obtained results indicate that the cause of both the temperature and the character of the spin-reorientation transition is a competition between the second and fourth …
Magnetic susceptibility, specific heat, and muon spin relaxation ($μ$SR) measurements have been performed on a newly synthesized three-dimensional sandglass-type lattice Tm$_3$SbO$_7$, where two inequivalent sets of non-Kramers Tm$^{3+}$ ions (Tm$^{3+}_1$ and Tm$^{3+}_2)$ show crystal electrical field effect at different temperature ranges. The existence of an ordered or a glassy state down to 0.1~K in zero field is excluded. The low-energy properties of Tm$_3$SbO$_7$ are dominated by the lowest non-Kramers quasi-doublet of $\rm Tm^{3+}_1$, and the energy splitting is regarded as an intrinsic …
We consider a class of d- and f-electron systems in which dipolar-octupolar Kramers doublets arise on the sites of the pyrochlore lattice. For such doublets, two components of the pseudospin transform like a magnetic dipole, while the other transforms like a component of the magnetic octupole tensor. Based on a symmetry analysis, we construct and study models of dipolar-octupolar doublets in itinerant and localized limits. In both limits, the resulting models are of surprisingly simple form. In the itinerant limit, we find topological insulating behavior. In the localized limit, the most gener…
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…
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…
We study the U(1) quantum spin liquid on the pyrochlore spin ice systems. For the non-Kramers doublets such as Pr$^{3+}$ and Tb$^{3+}$, we point out that the inelastic neutron scattering not only detects the low-energy gauge photon, but also contains the continuum of the "magnetic monopole" excitations. Unlike the spinons, these "magnetic monopoles" are purely of quantum origin and have no classical analogue. We further point out that the "magnetic monopole" experiences a background dual "$π$" flux due to the spin-1/2 nature of the local moment when the "monopole" hops on the dual diamond latt…
We predict the existence of vibrational Andreev bound states in deformable magnetic molecules on superconducting surfaces. We discuss the Anderson impurity model with electron-phonon coupling to a realistic anharmonic vibrational mode that modulates the tunneling barrier and show that the vibronic features are spectroscopically most visibile near the transition point between the Kondo-screened singlet and the unscreened doublet ground state. We find competing tendencies between phonon hardening due to anharmonicity and softening due to coupling to electrons, contrary to the Anderson-Holstein m…
The orthoperovskites TbCoO$_3$ and DyCoO$_3$ with Co$^{3+}$ in a non-magnetic low-spin state have been investigated by neutron diffraction down to 0.25 K. Magnetic ordering is evidenced below $T_N=3.3$ K and 3.6 K, respectively, and the ordered arrangements are of canted type, A$_x$G$_y$ for TbCoO$_3$ and G$_x$A$_y$ for DyCoO$_3$ in Bertaut's notation. The experiments are confronted with the first-principle calculations of the crystal field and magnetism of Tb$^{3+}$ and Dy$^{3+}$ ions, located in the $Pbnm$ structure on sites of $C_s$ point symmetry. Both these ions exhibit an Ising behavior,…
We study the spin-phonon relaxation rate of both Kramers and non-Kramers molecular magnets in strongly diluted samples at low temperature. Using the "rotational" contribution to the spin-phonon Hamiltonian, universal formulae for the relaxation rate are obtained. Intriguingly, these formulae are all entirely expressed via measurable or \emph{ab initio} computable physical quantities. Moreover, they are also independent of the energy gaps to excited states involved in the relaxation process. These obtained expressions for direct and Raman processes offer an easy way to determine the lowest limi…
We measured the reflectivity of a single crystal of FeSi from the far-infrared to the visible region (50-20000 wavenumber), varying the temperature between 4 and 300 K. The optical conductivity function was obtained via Kramers-Kronig analysis. We observed a dirty metal-like behavior at room temperature and the opening of a gap of 70 meV at low temperature. The results of a group theoretical analysis of the lattice vibrational modes are presented and compared to the experimental data. Of the five optical phonons expected for this material only four have been observed in the far-infrared region…
Induced quantum magnetism on a triangular lattice of non-Kramers ions in PrMgAl11O19
Charles University, Faculty of Mathematics and Physics（查理大学数学物理学院）；Adam Mickiewicz University, Faculty of Physics and Astronomy（亚当·密茨凯维奇大学物理与天文学学院）；Institute of Physics of the Czech Academy of Sciences（捷克科学院物理研究所）；Adam Mickiewicz University, NanoBioMedical Centre（亚当·密茨凯维奇大学纳米生物医学中心）
The thermodynamic Bethe ansatz equations for the N = 6 Coqblin-Schrieffer model with crystal fields have been solved numerically. The realistic case of three Kramers doublets with arbitrary splittings has been studied for the first time. The specific heat has been calculated for representative combinations of the ionic energy splittings providing ample material for comparison with experimental results for Cerium impurities and compounds.
We theoretically study electric quadrupole orders in f-electron systems on the fcc lattice. Qudrupole degrees of freedom $O_{20}$ and $O_{22}$ originate in the non-Kramers doublet ground state $Γ_3$ of ion with $f^2$ electron configuration. For discussing quadrupole orders, we use a minimal model with isotropic ($J$) and anisotropic ($K$) nearest-neighbor interactions, and determine the phase diagram using a four-site mean-field approximation at zero and finite temperatures. Quadrupoles couple the $Γ_3$ doublet to the singlet excited state $Γ_1$, and its effects on canting antiferro orders are…
The ground ytterbium doublet in h-YbMnO3 and the related low-temperature peculiarities of the compound
Institute of Spectroscopy, Russian Academy of Sciences（俄罗斯科学院光谱研究所）；Key Laboratory of Materials Physics, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences（中国科学院合肥物质科学研究院固体物理研究所材料物理重点实验室）
Frequency and dc magnetic field dependences of dynamic susceptibility in diluted paramagnets LiYF$_4$:Ho$^{3+}$ have been measured at liquid helium temperatures in the ac and dc magnetic fields parallel to the symmetry axis of a tetragonal crystal lattice. Experimental data are analyzed in the framework of microscopic theory of relaxation rates in the manifold of 24 electron-nuclear sublevels of the lowest non-Kramers doublet and the first excited singlet in the Ho$^{3+}$ ground multiplet $^5I_8$ split by the crystal field of S$_4$ symmetry. The one-phonon transition probabilities were compute…
The rare-earth magnet TmMgGaO$_{4}$ is proposed to be an intrinsic quantum Ising magnet described by the antiferromagnetic transverse field Ising model (TFIM) on a triangular lattice, where the relevant degrees of freedom are the non-degenerate dipole-multipole doublets of the Tm$^{3+}$ ions and the transverse field has an intrinsic origin from the weak splitting of the doublet. We compare this special doublet of Tm$^{3+}$ with the dipole-octupole Kramers doublet. We study the proposed effective model for the Tm-based triangular lattice and consider the effects of external magnetic fields and …
Inelastic neutron scattering measurement is performed on a breathing pyrochlore antiferromagnet Ba3Yb2Zn5O11. The observed dispersionless excitations are explained by a crystalline electric field (CEF) Hamiltonian of Kramers ion Yb3+ of which the local symmetry exhibits C3v point group symmetry. The magnetic susceptibility previously reported is consistently reproduced by the energy scheme of the CEF excitations. The obtained wave functions of the ground state Kramers doublet exhibit the planer-type anisotropy. The result demonstrates that Ba3Yb2Zn5O11 is an experimental realization of breathi…
Reflection and transmission as a function of temperature have been measured on a single crystal of the magnetoelectric ferrimagnetic compound Cu$_{2}$OSeO$_{3}$ utilizing light spanning the far infrared to the visible portions of the electromagnetic spectrum. The complex dielectric function and optical properties were obtained via Kramers-Kronig analysis and by fits to a Drude-Lortentz model. The fits of the infrared phonons show a magnetodielectric effect near the transition temperature ($T_{c}\sim 60$~K). Assignments to strong far infrared phonon modes have been made, especially those exhibi…
The ternary uranium compound UCu$_2$Sn with a hexagonal ZrPt$_2$Al-type structure shows a phase transition at 16 K. We reported previously that huge lattice-softening is accompanied by the phase transition, which originates from ferroquadrupolar ordering of the ground state non-Kramers doublet $Γ_5$. A macroscopic strain, which is expected to emerge spontaneously, was not detected by powder X-ray diffraction in the temperature range between 4.2 and 300 K. To search the spontaneous strain, we have carried out thermal expansion measurements on a single-crystalline sample along the $a$, $b$ and $…
In order to clarify possible multipole states of Sm-based filled skutterudite compounds, we investigate multipole susceptibility of a multiorbital Anderson model dynamically coupled with Jahn-Teller phonons by using a numerical renormalization group method. Here we take a procedure to maximize the multipole susceptibility matrix to determine the multipole state. When the electron-phonon coupling term is simply ignored, it is found that the dominant multipole state is characterized by 2u octupole for the $Γ_{67}^-$ quartet ground state, while the low-temperature phase is governed by magnetic fl…
The existence of CEF states and the magnetism in conducting compounds NdAl2, UPd2Al3 and YbRh2Si2 is discussed. We point out that in metallic compounds localized crystal-field states coexist with conduction electrons. These compounds are physical realization of an anisotropic spin liquid, which in case of the atomic-like configuration with an odd number of f electrons, is unstable with respect to spin fluctuations for T->0K. YbRh2Si2 is discussed as a compound with the Kramers doublet ground state with a very low magnetic ordering temperature being a reason for the quantum critical point pheno…
We theoretically investigate electronic states and physical properties in a two-channel Anderson lattice model to understand the non-Fermi liquid behaviors observed in PrV$_2$Al$_{20}$ and PrIr$_2$Zn$_{20}$ whose ground state of the crystalline electric field for local $f$-electron is the $Γ_3$ non-Kramers doublet of $f^2$-configuration and excited state is the $Γ_7$ Kramers doublet of $f^1$-configuration. We use the expansion from the limit of large degeneracy $N$ of the ground state ($1/N$-expansion), with $N$ being the spin-orbital degeneracy. Inclusion of the self-energy of the conduction …
