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Register a new userStructural anomalies, spin transitions and charge disproportionation in LnCoO3
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The diamagnetic-paramagnetic and insulator-metal transitions in LnCoO3 perovskites (Ln = La, Y, rare earths) are reinterpreted and modeled as a two-level excitation process. In distinction to previous models, the present approach can be characterized as a LS-HS-IS (low-high-intermediate spin) scenario. The first level is the local excitation of HS Co3+ species in the LS ground state. The second excitation is based on the interatomic electron transfer between the LS/HS pairs, leading finally to a stabilization of the metallic phase based on IS Co3+. The model parameters have been quantified for Ln = La, Pr and Nd samples using the powder neutron diffraction on the thermal expansion of Co-O bonds, that is associated with the two successive spin transitions. The same model is applied to interpret the magnetic susceptibility of LaCoO3 and YCoO3.
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A powder X-ray diffraction study, combined with the magnetic susceptibility and electric transport measurements, was performed on a series of LnCoO3 perovskites (Ln = Y, Dy, Gd, Sm, Nd, Pr and La) over a temperature range 100 - 1000 K. A non-standard temperature dependence of the observed thermal expansion was modelled as a sum of three contributions: (1) Weighted sum of lattice expansions of the cobaltite in the diamagnetic low spin state and in the intermediate (IS) or high (HS) spin state. (2) An anomalous expansion due to the increasing population of excited (IS or HS) states of Co3+ ions at the course of the diamagnetic-paramagnetic transition. (3) An anomalous expansion due to excitations of Co3+ ions to another paramagnetic state accompanied by an insulator-metal transition. The anomalous expansion is governed by parameters that are found to vary linearly with the Ln ionic radius. In the case of the first magnetic transition it is the energy splitting E between the ground low spin state and the excited state, presumably the intermediate spin state. The energy splitting E, determined by a fit of magnetic susceptibility, decreases with temperature. The values of E determined for LaCoO3 and YCoO3 at T = 0 K as 164 K and 2875 K, respectively, fall to zero at T = 230 K for LaCoO3 and 860 K for YCoO3. The second anomalous expansion connected with a simultaneous magnetic and insulator-metal transition is characterized by its center at T = 535 K for LaCoO3 and 800 K for YCoO3. The change of the unit cell volume during each transition is independent on the Ln cation and is about 1% in both cases.
The strength and effect of Coulomb correlations in the (superconducting when hydrated) x~1/3 and ``enhanced x~2/3 regimes of Na(x)CoO2 are evaluated using the correlated band theory LDA+U method. Our results, neglecting quantum fluctuations, are: (1) allowing only ferromagnetic order, there is a critical U_c = 3 eV, above which charge disproportionation occurs for both x=1/3 and x=2/3, (2) allowing antiferromagnetic order at x=1/3, U_c drops to 1 eV for disproportionation, (3) disproportionation and gap opening occur simultaneously, (4) in a Co(3+)-Co(4+) ordered state, antiferromagnetic coupling is favored over ferromagnetic, while below U_c ferromagnetism is favored. Comparison of the calculated Fermi level density of states compared to reported linear specific heat coefficients indicates enhancement of the order of five for x~0.7, but negligible enhancement for x~0.3. This trend is consistent with strong magnetic behavior and local moments (Curie-Weiss susceptibility) for x>0.5 while there no magnetic behavior or local moments reported for x<0.5. We suggest that the phase diagram is characterized by a crossover from effective single-band character with U >> W for x>0.5 into a three-band regime for x<0.5, where U --> U_eff <= U/sqrt(3) ~ W and correlation effects are substantially reduced.
Gen Shirane began studying ferroelectrics while he was still based in Japan in the early 1950s. It was therefore natural that when he arrived at Brookhaven and began specialising in neutron scattering that he would devote much of his energy and expertise studying structural phase transitions. We review the ground breaking experiments that showed the behaviour of antiferroelectrics and ferroelectrics were reasonably described in terms of the soft mode concept of structural phase transitions. This work lead directly to Gen being awarded the Buckley prize and, jointly with John Axe, awarded the Warren prize. We then describe his work on incommensurate phase transitions and in particular how the giant Kohn anomalies are responsible for the structural instabilities in one-dimensional metals. Finally Gen carefully investigated the central peak and the two-length scale phenomena that occur at most if not all transitions. Due to Gens elegant experimental work we know a great deal about both of these effects but in neither case is theory able to explain all of his results
We investigate the structural and magnetic phase transitions in EuTi1-xNbxO3 with synchrotron powder X-ray diffraction (XRD), resonant ultrasound spectroscopy (RUS), and magnetization measurements. Upon Nb-doping, the Pm-3m to I4/mcm structural transition shifts to higher temperatures and the room temperature lattice parameter increases while the magnitude of the octahedral tilting decreases. In addition, Nb substitution for Ti destabilizes the antiferromagnetic ground state of the parent compound and long range ferromagnetic order is observed in the samples containing more than 10% Nb. The structural transition in pure and doped compounds is marked by a step-like softening of the elastic moduli in a narrow temperature interval near TS, which resembles that of SrTiO3 and can be adequately modeled using the Landau free energy model employing the same coupling between strain and octahedral tilting order parameter as previously used to model SrTiO3.
Neutron diffraction studies as a function of temperature on solid solutions of MnSe and MnTe in the Se rich region are presented. Interestingly as Te is doped in MnSe, the structural transformation to NiAs phase diminishes, both in terms of % fraction of compound as well as in terms of transition temperature. In MnTe$_{0.3}$Se$_{0.7}$, the NaCl to NiAs phase transformation occurs at about 40K and although it is present at room temperature in MnTe$_{0.5}$Se$_{0.5}$, its volume fraction is only about 10% of the total volume of sample. The magnetic ordering temperature of the cubic phase decreases with increasing Te content while the hexagonal phase orders at the same temperature as in MnSe. Anomalies in thermal evolution of lattice parameters at magnetic ordering as well as structural transition temperatures indicate presence of magnetostructural coupling in these compounds.
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