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Register a new userSpin state of Co$^{3+}$ in LaCo$_{1-x}$Rh$_{x}$O$_{3}$ investigated by structural phenomena
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Neutron diffraction for a polycrystalline sample of LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$ and synchrotron x-ray diffraction for polycrystalline samples of LaCo$_{0.9}$Rh$_{0.1}$O$_{3}$ and LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$ have been carried out in order to investigate the structural properties related with the spin state of Co$^{3+}$ ions. We have found that the values of the Co(Rh)-O bond lengths in the Co(Rh)O$_{6}$ octahedron of LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$ are nearly identical at 10 K. The lattice volume for the Rh$^{3+}$ substituted samples decreases with the thermal expansion coefficient similar to that of LaCoO$_{3}$ from room temperature, and ceases to decrease around 70 K. These experimental results favor a mixed state consisting of the high-spin-state and low-spin-state Co$^{3+}$ ions, and suggest that the high-spin-state Co$^{3+}$ ions are thermally excited in addition to those pinned by the substituted Rh$^{3+}$ ions.
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The rhodium doping in the LaCo$_{1-x}$Rh$_{x}$O$_3$ perovskite series ($x=0.02-0.5$) has been studied by X-ray diffraction, electric transport and magnetization measurements, complemented by electronic structure GGA+U calculations in supercell for different concentration regimes. No charge transfer between Co$^{3+}$ and Rh$^{3+}$ is evidenced. The diamagnetic ground state of LaCoO$_3$, based on Co$^{3+}$ in low-spin (LS) state, is disturbed even by a small doping of Rh. The driving force is the elastic energy connected with incorporation of a large Rh$^{3+}$ cation into the matrix of small LS Co$^{3+}$ cations, which is relaxed by formation of large Co$^{3+}$ in high-spin (HS) state in the next-nearest sites to the inserted Rh atom. With increasing temperature, the population of Co$^{3+}$ in HS state increases through thermal excitation, and a saturated phase is obtained close to room temperature, consisting of a nearest-neighbor correlation of small (LS Co$^{3+}$) and large (HS Co$^{3+}$ and LS Rh$^{3+}$) cations in a kind of double perovskite structure. The stabilizing role of elastic and electronic energy contributions is demonstrated in supercell calculations for dilute Rh concentration compared to other dopants with various trivalent ionic radius.
Ba$_3$Mn$_2$O$_8$ is a geometrically frustrated spin dimer compound. We investigate the effect of site disorder on the zero field phase diagram of this material by considering the solid solution Ba$_{3}$(Mn$_{1-x}$V$_{x}$)$_{2}$O$_{8}$, where nonmagnetic V$^{5+}$ ions partially substitute magnetic Mn$^{5+}$ ions. This substitution results in unpaired $S=1$ moments for half-substituted dimers, which are ungapped and therefore susceptible to types of magnetic order not present in the parent compound. AC susceptibility measurements of compositions between $x=0.046$ and $x=0.84$ show a sharp frequency- and composition-dependent kink at temperatures below 210mK, suggesting that unpaired spins form a spin glass. The case for a glassy state is made clearer by the absence of any sharp features in the specific heat. However, Ba$_{3}$(Mn$_{1-x}$V$_{x}$)$_{2}$O$_{8}$ is not a paradigmatic spin glass. Whereas both the freezing temperature and the Weiss temperature (determined from susceptibility above 1K) vary strongly as a function of composition, the heat capacity per unpaired spin is found to be insensitive (above the glass transition) to the density of unpaired spins for the broad regime $0.18leq x leq 0.84$. This surprising result is consistent with a scenario in which nearest-neighbor unpaired spins form local, possibly fluctuating, spin-singlets prior to the eventual spin freezing. The spin glass state is only found for temperatures below the energy scale of single-ion anisotropy, suggestive this plays a significant role in determining the eventual ground state. Possible ground states in the dilute limit ($x < 0.04$ and $x > 0.9$) are also discussed.
We report the structural and magnetic properties of the 4}textit{textcolor{black}{d }}textcolor{black}{(M = Rh) based and 5}textit{textcolor{black}{d }}textcolor{black}{(M = Ir) based systems Ba$_{3}$M$_{x}$Ti$_{3-x}$O$_{9}$ (nominally $x$ = 0.5, 1). The studied compositions were found to crystallize in a hexagonal structure with the centrosymmetric space group }$P6_{3}/mmc$.textcolor{black}{{} The structures comprise of A$_{2}$O$_{9}$ polyhedra (with the A site (possibly) statistically occupied by M and Ti) in which pairs of transition metal ions are stacked along the crystallographic }textit{textcolor{black}{c}}textcolor{black}{-axis. These pairs form triangular bilayers in the $ab$-plane. The magnetic Rh and Ir ions occupy these bilayers, diluted by Ti ions even for $x$ = 1. These bilayers are separated by a triangular layer which is dominantly occupied by Ti ions. From magnetization measurements we infer strong antiferromagnetic couplings for all of the materials but the absence of any spin-freezing or spin-ordering down to 2~K. Further, specific heat measurements down to 0.35~K show no sign of a phase transition for any of the compounds. Based on these thermodynamic measurements we propose the emergence of a quantum spin liquid ground state for Ba$_{3}$Rh$_{0.5}$Ti$_{2.5}$O$_{9}$, and Ba$_{3}$Ir$_{0.5}$Ti$_{2.5}$O$_{9}$, in addition to the already reported Ba$_{3}$IrTi$_{2}$O$_{9}$. }
We report thermal-expansion, lattice-constant, and specific-heat data of the series La_1-xA_xCoO_3 for 0<= x <= 0.30 with A = Ca, Sr, and Ba. For the undoped compound LaCoO_3 the thermal-expansion coefficient alpha(T) exhibits a pronounced maximum around T=50K caused by a temperature-driven spin-state transition from a low-spin state of the Co^{3+$ ions at low towards a higher spin state at higher temperatures. The partial substitution of the La^{3+} ions by divalent Ca^{2+}, Sr^{2+}, or Ba^{2+} ions causes drastic changes in the macroscopic properties of LaCoO3. The large maximum in alpha(T) is suppressed and completely vanishes for x> 0.12. For A = Ca three different anomalies develop in alpha(T) with further increasing x, which are visible in specific-heat data as well. Together with temperature-dependent x-ray data we identify several phase transitions as a function of the doping concentration x and temperature. From these data we propose an extended phase diagram for La_1-xCa_xCoO_3.
We study magnetic and multiferroic behavior in Ca$_3$Co$_{2-x}$Mn$_{x}$O$_6$ ($x sim$0.97) by high-field measurements of magnetization ($M$), magnetostriction ($L$($H$)/$L$), electric polarization ($P$), and magnetocaloric effect. This study also gives insight into the zero and low magnetic field magnetic structure and magnetoelectric coupling mechanisms. We measured $M$ and $Delta$$L$/$L$ up to pulsed magnetic fields of 92 T, and determined the saturation moment and field. On the controversial topic of the spin states of Co$^{2+}$ and Mn$^{4+}$ ions, we find evidence for $S$ = 3/2 spins for both ions with no magnetic field-induced spin-state crossovers. Our data also indicate that Mn$^{4+}$ spins are quasi-isotropic and develop components in the $ab$-plane in applied magnetic fields of 10 T. These spins cant until saturation at 85 T whereas the Ising Co$^{2+}$ spins saturate by 25 T. Furthermore, our results imply that mechanism for suppression of electric polarization with magnetic fields near 10 T is flopping of the Mn$^{4+}$ spins into the $ab$-plane, indicating that appropriate models must include the coexistence of Ising and quasi-isotropic spins.
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