NMR study of the magnetic and metal-insulator transitions in Na0.5CoO2: a nesting scenario

Co and Na NMR are used to probe the local susceptibility and charge state of the two Co sites of the Na-ordered orthorhombic Na(0.5)CoO(2). Above T(N) = 86 K, both sites display a similar T dependence of the spin shift, suggesting that there is no charge segregation into Co(3+) and Co(4+) sites. Below T(N), the magnetic long range commensurate order found is only slightly affected by the metal-insulator transition at T(MIT) = 51 K. Furthermore, the electric field gradient at the Co site does not change at these transitions, indicating the absence of charge ordering. All these observations can be explained by successive spin-density wave induced by two nestings of the Fermi surface specific to the x = 0.5 Na ordering.     

Disproportionation, metal-insulator transition, and critical interaction strength in Na(1/2)CoO2

Charge disproportionation (CD) and spin differentiation in Na(1/2)CoO2 are studied using the correlated band local-density approximation + Hubbard U (LDA+U) approach. The simultaneous CD and gap opening seen previously is followed in detail through a first-order charge disproportionation transition 2Co(3.5+)-->Co3++Co4+. Disproportionation in the Co a(g) orbital results in half of the ions (Co3+) becoming electronically and magnetically dead, transforming the quarter-filled a(g) system into a half-filled subsystem that subsequently undergoes the observed charge ordering or metal-insulator transition. Comparing with data in the x approximately 0.3 regime suggests the system has moved into the multiband regime where the effective Coulomb repulsion U-->U(eff)=U/sqrt[3] strongly lessens correlation effects.     

Metamagnetic phase transitions induced by static and pulsed fields in (Sm0.5Gd0.5)0.55Sr0.45MnO3 ceramics

It has been found that the magnetic susceptibility of (Sm_0.5Gd_0.5)_0.55Sr_0.45MnO₃ ceramic samples in zero external magnetic field exhibits a sharp peak near the temperature of 48.5 K with a small temperature hysteresis that does not depend on the frequency of measurements and is characteristic of the phase transition to an antiferromagnetic state with a long-range charge orbital ordering, which is accompanied by an increase in the magnetic susceptibility with a decrease in the temperature. The magnetization isotherms in static and pulsed magnetic fields at temperatures below 60 K demonstrate the occurrence of an irreversible metamagnetic transition to a homogeneous ferromagnetic state with a critical transition field independent of the measurement temperature, which, apparently, is associated with the destruction of the insulating state with a long-range charge ordering. In the temperature range 60 K ?? T ?? 150 K, the ceramic samples undergo a magnetic-field-induced reversible phase transition to the ferromagnetic state, which is similar to the metamagnetic transition in the low-temperature phase and is caused by the destruction of local charge/orbital correlations. With an increase in the temperature, the critical transition fields increase almost linearly and the field hysteresis disappears. Near the critical fields of magnetic phase transitions, small ultra-narrow magnetization steps have been revealed in pulsed fields with a high rate of change in the magnetic field of ??400 kOe/??s.     

Independent freezing of charge and spin dynamics in La1.5Sr0.5CoO4

We present elastic and quasielastic neutron scattering measurements characterizing peculiar short-range charge-orbital and spin order in the layered perovskite material La1.5Sr0.5CoO4. We find that below T(c) approximately 750 K holes introduced by Sr doping lose mobility and enter a statically ordered charge glass phase with loosely correlated checkerboard arrangement of empty and occupied d(3z(2)-r(2)) orbitals ( Co3+ and Co2+). The dynamics of the resultant mixed spin system is governed by the anisotropic nature of the crystal-field Hamiltonian and the peculiar exchange pattern produced by the orbital order. It undergoes a spin freezing transition at a much lower temperature, T(s) less, similar30 K.     

Magnetic-field switching of crystal structure in an orbital-spin-coupled system: MnV2O4

We studied the magnetic and structural properties of spinel MnV2O4, which has S=5/2 spin with no orbital degrees of freedom on the Mn2+ site and S=1 spin and three orbital degrees of freedom on the V3+ site. We found that the ferrimagnetic ordering at TN=56.5K and the structural phase transition at Ts=53.5K are closely correlated in this compound and found a switching of crystal structure between cubic and tetragonal phases by the magnetic field. This phenomenon can be explained by the coupling between orbital and spin degrees of freedom in the t2g states of the V site.     

Orbital ordering and spin-ladder formation in La2RuO5

The semiconductor-semiconductor transition of La2RuO5 is studied by means of augmented spherical wave electronic structure calculations as based on density-functional theory and the local density approximation. This transition has lately been reported to lead to orbital ordering and a quenching of the local spin magnetic moment. Our results hint towards an orbital ordering scenario which, markedly different from the previously proposed scheme, preserves the local S=1 moment at the Ru sites in the low-temperature phase. The unusual magnetic behavior is interpreted by the formation of spin ladders, which result from the structural changes occurring at the transition and are characterized by antiferromagnetic coupling along the rungs.     

Possible electron-phonon interaction-driven microscopic origin of the phase transitions in β-Na 0.33 V 2 O 5 and analogues

The microscopic origin of the various phase transitions which have been observed in g-Na 0.33 V 2 O 5 and its analogues can be explored experimentally by investigating the oxygen isotope effect on the phase transition temperatures. An absent oxygen isotope effect on the sodium-ordering transition would point to an antiferroelectrically driven instability, while a large isotope effect on the charge ordering and spin ordering transition temperatures would suggest the formation of a charge-density wave instability and phonon mediated long-range magnetic ordering. All instabilities can be attributed to strong electron-phonon interaction effects, which dominate the ground-state properties.     

Interplay of structural, magnetic and transport properties in thelayered Co-based perovskite LnBaCo 2 O 5 (Ln = Tb, Dy, Ho)

The oxygen deficient cobaltites LnBaCo₂O₅ (Ln = Tb, Dy, Ho) exhibit two successive crystallographic transitions at T _N ∼340 K and at T _CO ∼210 K. Whereas the first transition (P4/mmm to Pmmm) is related to the long-range antiferromagnetic ordering of the Co ions (spin ordering), the second transition (Pmmm to Pmmb) corresponds to the long-range ordering of the Co²⁺ and Co³⁺ species (charge ordering) occurring in 1:1 ratio in the structure. The charge ordered (CO) state was directly evidenced by the observation of additional superstructure peaks using neutron and electron diffraction techniques. The CO state was also confirmed indirectly from refinement of high resolution neutron diffraction data as well as from resistivity and DSC measurements. From the refined saturated magnetic moment values only, ∼3.7 and ∼2.7 , the electronic configuration of the Co ions in LnBaCo₂O₅ remains conjectural. Two pictures, with Co³⁺ ions either in intermediate spin state ( t ⁵ _2g e ¹ _g ) or in high spin state ( t ⁴ _2g e ² _g ), describe equally well our experimental data. In both cases, the observed magnetic structure can be explained using the qualitative Goodenough-Kanamori rules for superexchange. Finally, in contrast to the parent Ln = Y compound [Vogt et al. , Phys. Rev. Lett. 84, 2969 (2000)], we do not report any spin transition in LnBaCo₂O₅ (Ln = Tb, Dy, Ho). Received 13 December 2000     

Spin-singlet clusters in the ladder compound NaV2O5

The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.     

Static magnetic order in metallic K0.49CoO2

By means of muon-spin spectroscopy, we have found that K0.49CoO2 crystals undergo successive magnetic transitions from a high-T paramagnetic state to a magnetic ordered state below 60 K and then to a second ordered state below 16 K, even though K0.49CoO2 is metallic at least down to 4 K. An isotropic magnetic behavior and wide internal-field distributions suggest the formation of a commensurate helical spin density wave (SDW) state below 16 K, while a linear SDW state is likely to exist above 16 K. It was also found that exhibits a further transition at 150 K presumably due to a change in the spin state of the Co ions. Since the dependence of the internal-field below 60 K was similar to that for Na0.5CoO2, this suggests that magnetic order is more strongly affected by the Co valence than by the interlayer distance or interaction and/or the charge ordering.     

59Co NMR evidence for charge ordering below T_(CO) approximately 51 K in Na0.5CoO2

The CoO2 layers in NaxCoO2 may be viewed as a spin S=1/2 triangular-lattice doped with charge carriers. The underlying physics of the cobaltates is very similar to that of the high T_(c) cuprates. We will present unequivocal 59Co NMR evidence that below T_(CO) approximately 51 K, the insulating ground state of the itinerant antiferromagnet Na0.5CoO2 (T_(N) approximately 86 K) is induced by charge ordering.     

Charge-orbital ordering and Verwey transition in magnetite

Local density approximation + Hubbard U (LDA + U) band structure calculations reveal that magnetite (Fe3O4) forms an insulating charge-orbital-ordered state below the Verwey transition temperature. The calculated charge ordering is in good agreement with that inferred from recent experiments. We found an associated t(2g) orbital ordering on the octahedral Fe2+ sublattice. Such an orbital ordering results primarily from the on-site Coulomb interaction. This finding unravels such fundamental issues about the Verwey transition as the mechanism for the charge ordering and for the formation of the insulating gap, as well as the nonobedience of the Anderson's criterion for the charge ordering.     

Coherent magnetic oscillation in the spin ladder system alpha(')- NaV2O5

We report the first observation of coherent magnetic excitations in a spin ladder system NaV2O5 by using femtosecond time-domain spectroscopy. A pronounced coherent oscillation is observed at 127 cm(-1) (nearly twice the spin gap energy) and assigned to a two-magnon bound state, based on the temperature dependence of the intensity below the charge ordering phase transition at T(C) = 34 K. This mode can be observable only when circularly polarized light is used as a pump or a probe beam, suggesting that it corresponds to a spin-flip excitation from the singlet ground state. A phonon mode strongly coupled to the spin state is also found at 303 cm(-1).     

Charge ordering and magnetopolarons in Na0.82CoO2

Using spectral ellipsometry, we measured the dielectric function of a Na(0.82(2))CoO2 crystal that exhibits bulk antiferromagnetism with T(N)=19.8 K. We identify two prominent transitions as a function of temperature. The first one at 280 K involves marked changes of the electronic and lattice responses that are indicative of charge ordering in the CoO2 layers. The second transition occurs around T(N)=19.8 K and reveals sizable spin-charge coupling. The data are discussed in terms of charge ordering and formation of magnetopolarons due to a charge-induced spin-state transition of adjacent Co3+ ions.     

Verwey transition in spin polarization of field-emitted electrons from 〈1 1 0〉-oriented single crystal magnetite whisker

We measured temperature dependence of a spin polarization of field-emitted electrons from a single-crystalline magnetite (Fe₃O₄) whisker with 〈1 1 0〉 orientation. The spin polarization of emitted electrons began to increase above 130 K corresponding to the temperature of Verwey point (T_v). The increase is considered as reflection of the change of the spin state near the Fermi level due to the Verwey transition. Our experimental results support a localization of t_2g orbital electrons below the Verwey point and a model of charge ordering for magnetite.     

Unusual symmetries in the Kugel-Khomskii Hamiltonian

The Kugel-Khomskii Hamiltonian for cubic titanates describes spin and orbital superexchange interactions between d(1) ions having threefold degenerate t(2g) orbitals. Since orbitals do not couple along "inactive" axes, perpendicular to the orbital planes, the total number of electrons in |alpha> orbitals in any such plane and the corresponding total spin are both conserved. A Mermin-Wagner construction shows that there is no long-range spin ordering at nonzero temperatures. Inclusion of spin-orbit coupling allows such ordering, but even then the excitation spectrum is gapless due to a continuous symmetry. Thus, the observed order and gap require more symmetry breaking terms.     

Antiferromagnetic d-electron exchange via a spin-singlet pi-electron ground state in an organic conductor

Electron spin resonance reveals the spin behavior of conduction (pi) and localized (d) electrons in beta-(BDA-TTP)2MCl4 (M=Fe, Ga). Both the Ga3+(S=0) and Fe3+(S=5/2) compounds exhibit a metal-insulator transition at 113 K with the simultaneous formation of a spin-singlet ground state in the pi electron system of the donor molecules. The behavior is consistent with charge ordering in beta-(BDA-TTP)2MCl4 at the metal-insulator transition. At 5 K, the Fe3+ compound orders antiferromagnetically, even though the pi electrons, which normally would facilitate magnetic exchange, are localized nonmagnetic singlets.     

Evidence for a spin glass state in the intermetallic compounds Gd3Pd4−xPtx

Magnetic susceptability measurements in static fields have shown that the intermetallic compound Gd₃Pd_4?xPt_x exhibits a transition from antiferromagnetism for x = 3 to a spin glass state for x < 2 below 7.5 K. For x = 3 long-range ordering is established and for x = 2 both long-range ordering and the spin glass state are clearly present.     

Successive orbital ordering transitions in NaVO2

Physical property measurements on samples of triangular-lattice NaVO2 reveal two successive orbital ordering transitions. At 300 K, the structure is rhombohedral. At 98 K, the system undergoes a second-order transition to a monoclinic phase in which the in-plane V-V distances separate into four short and two long bonds, corresponding to orbital ordering of one electron per V3+. Below 93 K, there is a first-order transition to a second monoclinic phase with four long and two short V-V bonds, consistent with orbital ordering of two electrons per V3+. Long range magnetic ordering of 0.98(2)mu_(B) per V3+ (3d(2)) sets in at the 93 K structural transition. The orbital ordering relieves the geometric frustration and leads to a magnetically ordered ground state.     

Neutron powder diffraction investigation on the crystal and magnetic structure of (Ho(0.50+x)Ca(0.50-x))(Mn(1-x)Cr(x))O3

The crystal and magnetic structure of (Ho(0.50+x)Ca(0.50-x))(Mn(1-x)Cr(x))O(3) (x = 0.00, 0.01, 0.02, 0.03) has been investigated between 5 and 300 K by means of neutron powder diffraction followed by Rietveld refinement and dc magnetic measurements. During cooling an orthorhombic to monoclinic phase transition occurs on account of the charge and orbital ordering taking place in the Mn sub-lattice; at low temperature phase separation takes place and the main monoclinic phase coexists with a secondary orthorhombic phase, whose amount slightly increases with the increase of Cr content. Cr(3+) is not involved in orbital ordering or superexchange interactions. The charge and magnetic ordering are decoupled: the Mn moments order according to a CE-type structure in all samples.