We have synthesized a new spinel oxide LiRh2O4 with a mixed-valent configuration of Rh3+ and Rh4+. At room temperature it is a paramagnetic metal, but on cooling, a metal-insulator transition occurs and a valence bond solid state is formed below 170 K. We argue that the formation of valence bond solid is promoted by a band Jahn-Teller transition at 230 K and the resultant confinement of t2g holes within the xy band. The band Jahn-Teller instability is also responsible for the observed enhanced thermoelectric power in the orbital disordered phase above 230 K.
Vanadium spinels (ZnV_2O_4, MgV_2O_4, and CdV_2O_4) exhibit a sequence of structural and magnetic phase transitions, reflecting the interplay of lattice, orbital, and spin degrees of freedom. We offer a theoretical model taking into account the relativistic spin-orbit interaction, collective Jahn-Teller effect, and spin frustration. Below the structural transition, vanadium ions exhibit ferroorbital order and the magnet is best viewed as two sets of antiferromagnetic chains with a single-ion Ising anisotropy. Magnetic order, parametrized by two Ising variables, appears at a tetracritical point…
We have theoretically studied successive transitions in vanadium spinel oxides with (t_2g)^2 electron configuration. These compounds show a structural transition at ~ 50K and an antiferromagnetic transition at ~ 40K. Since threefold t_2g orbitals of vanadium cations are occupied partially and vanadiums constitute a geometrically-frustrated pyrochlore lattice, the system provides a particular example to investigate the interplay among spin, orbital and lattice degrees of freedom on frustrated lattice. We examine the models with the Jahn-Teller coupling and/or the spin-orbital superexchange inte…
The ground-state properties of the spin-1 antiferromagnetic Heisenberg model on the corner-sharing tetrahedra, pyrochlore lattice, is investigated. By breaking up each spin into a pair of 1/2-spins, the problem is reduced to the equivalent one of the spin-1/2 tetrahedral network in analogy with the valence bond solid state in one dimension. The twofold degeneracy of the spin-singlets of a tetrahedron is lifted by a Jahn-Teller mechanism, leading to a cubic to tetragonal structural transition. It is proposed that the present mechanism is responsible for the phase transition observed in the spin…
We present our theoretical results on the electronic state in vanadium spinel oxide AlV$_2$O$_4$. The material is a mixed-valent system with the average valence V$^{2.5+}$, and V cations constitute a frustrated pyrochlore structure. It shows a structural transition at $\sim 700$ K, leading to the formation of seven V-sites clusters -- heptamers. We study the electronic state of the heptamer by explicitly taking account of orbital degree of freedom as well as electron correlations. We show that the ground state of the heptamer for realistic parameters becomes spin-singlet because of strong $σ$-…
A systematic study using neutron diffraction and magnetic susceptibility are reported on Mn substituted ferrimagnetic inverse spinel Ti$_{1-x}$Mn$_{x}$Co$_2$O$_4$ in the temperature interval 1.6 K $\leq$ $T$ $\leq$ 300 K. Our neutron diffraction study reveals cooperative distortions of the $T$O$_6$ octahedral for all the Jahn-Teller active ions $T$ = Mn$^{3+}$, Ti$^{3+}$ and Co$^{3+}$, which are confirmed by the X-ray photoelectron spectroscopy. Two specific compositions ($x$ = 0.2 and 0.4) have been chosen because of their unique features: noncollinear Yafet-Kittel type ordering, and weak tet…
We propose a scenario for the two phase transitions in $A$V$_2$O$_4$ ($A$=Zn, Mg, Cd), based on an effective spin-orbital model on the pyrochlore lattice. At high temperatures, spin correlations are strongly frustrated due to the lattice structure, and the transition at $\sim$50 [K] is an orbital order, supported by Jahn-Teller lattice distortion. This orbital order introduces spatial modulation of spin exchange couplings depending on the bond direction. This partially releases the frustration, and leads to a spin order at $\sim$40 [K]. We also study the stable spin configuration by taking acc…
We report the observation of an antipolar phase in cubic GaNb$_4$S$_8$ driven by an unconventional microscopic mechanism, the cooperative Jahn-Teller effect of Nb$_4$S$_4$ molecular clusters. The assignment of the antipolar nature is based on sudden changes in the crystal structure and a strong drop of the dielectric constant at $T_\mathrm{JT}=31$\,K, also indicating the first-order nature of the transition. In addition, we found that local symmetry lowering precedes long-range orbital ordering, implying the presence of a dynamic Jahn-Teller effect in the cubic phase above $T_\mathrm{JT}$. Bas…
We posit that there exist deep and fundamental relationships between the above seemingly very different materials. The carrier concentration-dependences of the electronic behavior in the conducting organic charge-transfer solids and layered cobaltates are very similar. These dependences can be explained within a single theoretical model, - the extended Hubbard Hamiltonian with significant nearest neighbor Coulomb repulsion. Interestingly, superconductivity in the cobaltates seems to be restricted to bandfilling exactly or close to one-quarter, as in the organics. We show that dynamic Jahn-Tell…
We review the mechanism of spin-lattice coupling in relieving the geometrical frustration of pyrochlore antiferromagnets, in particular spinel oxides. The tetrahedral unit, which is the building block of the pyrochlore lattice, undergoes a spin-driven Jahn-Teller instability when lattice degrees of freedom are coupled to the antiferromagnetism. By restricting our considerations to distortions which preserve the translational symmetries of the lattice, we present a general theory of the collective spin-Jahn-Teller effect in the pyrochlore lattice. One of the predicted lattice distortions breaks…
Ultrasound velocity measurements of magnesium chromite spinel MgCr$_2$O$_4$ reveal elastic anomalies in the paramagnetic phase that are characterized as due to geometrical frustration. The temperature dependence of the tetragonal shear modulus $(C_{11}-C_{12})/2$ exhibits huge Curie-type softening, which should be the precursor to spin Jahn-Teller distortion in the antiferromagnetic phase. The trigonal shear modulus $C_{44}$ exhibits nonmonotonic temperature dependence with a characteristic minimum at $\sim$50 K, indicating a coupling of the lattice to dynamical molecular spin state. These res…
Dynamical properties of the lattice structure was studied by optical spectroscopy in ACr2O4 chromium spinel oxide magnetic semiconductors over a broad temperature region of T=10-335K. The systematic change of the A-site ions (A=Mn, Fe, Co, Ni and Cu) showed that the occupancy of 3d orbitals on the A-site, has strong impact on the lattice dynamics. For compounds with orbital degeneracy (FeCr2O4, NiCr2O4 and CuCr2O4), clear splitting of infrared-active phonon modes and/or activation of silent vibrational modes have been observed upon the Jahn-Teller transition and at the onset of the subsequent …
We present our theoretical results on the mechanism of two transitions in vanadium spinel oxides $A$V$_2$O$_4$ ($A$=Zn, Mg, or Cd) in which magnetic V cations constitute a geometrically-frustrated pyrochlore structure. We have derived an effective spin-orbital-lattice coupled model in the strong correlation limit of the multiorbital Hubbard model, and applied Monte Carlo simulation to the model. The results reveal that the higher-temperature transition is a layered antiferro-type orbital ordering accompanied by tetragonal Jahn-Teller distortion, and the lower-temperature transition is an antif…
Magnetite (Fe$_{3}$O$_{4}$) is a mixed valent system where electronic conductivity occurs on the B-site (octahedral) iron sublattice of the spinel structure. Below $T_{V}=122$ K, a metal-insulator transition occurs which is argued to arise from the charge ordering of 2+ and 3+ iron valences on the B-sites (Verwey transition). Inelastic neutron scattering measurements show that optical spin waves propagating on the B-site sublattice ($\sim$80 meV) are shifted upwards in energy above $T_{V}$ due to the occurrence of B-B ferromagnetic double exchange in the mixed valent metallic phase. The double…
Possible routes to superconductivity in the surface layers of V-doped Mg$_{1-δ}$Ti$_2$O$_4$ through multiple charge transfers and suppression of Jahn-Teller activity
Ultrasound velocity measurements of cubic spinel GeCo$_2$O$_4$ in single crystal were performed for the investigation of shear and compression moduli. The shear moduli in the paramagnetic state reveal an absence of Jahn-Teller activity despite the presence of orbital degeneracy in the Co$^{2+}$ ions. Such a Jahn-Teller inactivity indicates that the intersite orbital-orbital interaction is much stronger than the Jahn-Teller coupling. The compression moduli in the paramagnetic state near the N$\acute{e}$el temperature $T_N$ reveal that the most relevant exchange path for the antiferromagnetic tr…
Reproducing the electronic structure of AM$_4$X$_8$ lacunar spinels with a breathing pyrochlore lattice is a great theoretical challenge due to the interplay of various factors. The character of the M$_4$X$_4$ cluster orbitals is critically influenced by the Jahn-Teller instability, the spin-orbit interaction, and also by the magnetic state of the clusters. Consequently, to reproduce the narrow-gap semiconducting nature of these moderately correlated materials requires advanced approaches, since the strength of the inter-cluster hopping is strongly affected by the character of the cluster orbi…
We present the results of broadband dielectric spectroscopy of GaMo$_4$S$_8$, a lacunar spinel system that recently was shown to exhibit non-canonical, orbitally-driven ferroelectricity. Our study reveals complex relaxation dynamics of this multiferroic material, both above and below its Jahn-Teller transition at T$_{\textrm{JT}}=47$ K. Above T$_{\textrm{JT}}$, two types of coupled dipolar-orbital dynamics seem to compete: relaxations within cluster-like regions with short-range polar order like in relaxor ferroelectrics and critical fluctuations of only weakly interacting dipoles, the latter …
The mixed-valent spinel LiV$_{2}$O$_{4}$ is known as the first oxide heavy-fermion system. There is a general consensus that a subtle interplay of charge, spin, and orbital degrees of freedom of correlated electrons plays a crucial role in the enhancement of quasi-particle mass, but the specific mechanism has remained yet elusive. A charge-ordering (CO) instability of V$^{3+}$ and V$^{4+}$ ions that is geometrically frustrated by the V pyrochlore sublattice from forming a long-range CO down to $T$ = 0 K has been proposed as a prime candidate for the mechanism. To uncover the hidden CO instabil…
Selenium and tellurium are among the few elements that form $AB$O$_3$ perovskite structures with a four valent ion in the $A$ site. This leads to highly distorted structures and unusual magnetic behavior. Here we investigate the Co and Ni selenite and tellurite compounds, CoSeO$_3$, CoTeO$_3$, NiSeO$_3$ and NiTeO$_3$ using first principles calculations. We find an interplay of crystal field and Jahn-Teller distortions that underpin the electronic and magnetic properties. While all compounds are predicted to show an insulating G-type antiferromagnetic ground state, there is a considerable diffe…
The spinel FeV2O4 is known to exhibit peculiar physical properties, which is generally ascribed to the unusual presence of two cations showing a pronounced interplay between spin, orbital and lattice degrees of freedom (Fe2+ and V3+ on the tetrahedral and octahedral sites, respectively). The present work reports on an experimental re-investigation of this material based on a broad combination of techniques, including x-ray diffraction, energy dispersive and Mössbauer spectroscopies, as well as magnetization, heat capacity, dielectric and polarization measurements. Special attention was firstly…
We present our theoretical and numerical results on thermodynamic properties and the microscopic mechanism of two successive transitions in vanadium spinel oxides $A$V$_2$O$_4$ ($A$=Zn, Mg, or Cd) obtained by Monte Carlo calculations of an effective spin-orbital-lattice model in the strong correlation limit. Geometrical frustration in the pyrochlore lattice structure of V cations suppresses development of spin and orbital correlations, however, we find that the model exhibits two transitions at low temperatures. First, a discontinuous transition occurs with an orbital ordering assisted by the …
CaBaFe4O7 is a mixed-valent transition metal oxide having both Fe2+ and Fe3+ ions in tetrahedral coordination. Here we characterize its magnetic properties by magnetization measurements and investigate its local electronic structure using soft x-ray absorption spectroscopy at the Fe L2,3 edges, in combination with multiplet cluster and spin-resolved band structure calculations. We found that the Fe2+ ion in the unusual tetrahedral coordination is Jahn-Teller active with the high-spin e^2 (up) t2^3 (up) e^1 (down) configuration having a x^2-y^2-like electron for the minority spin. We deduce tha…
Magnetic spinels (with chemical formula $AX_{2}$O$_{4}$, with $X$ a 3$d$ transition metal ion) that also have an orbital degeneracy are Jahn-Teller active and hence possess a coupling between spin and lattice degrees of freedom. At high temperatures, MgV$_{2}$O$_{4}$ is a cubic spinel based on V$^{3+}$ ions with a spin $S$=1 and a triply degenerate orbital ground state. A structural transition occurs at T$_{OO}$=63 K to an orbitally ordered phase with a tetragonal unit cell followed by an antiferromagnetic transition of T$_{N}$=42 K on cooling. We apply neutron spectroscopy in single crystals …
