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Register a new userEvidence for a Low-Spin to Intermediate-Spin State Transition in LaCoO3
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We present measurements of the magnetic susceptibility and of the thermal expansion of a LaCoO$_3$ single crystal. Both quantities show a strongly anomalous temperature dependence. Our data are consistently described in terms of a spin-state transition of the Co$^{3+}$ ions with increasing temperature from a low-spin ground state to an intermediate-spin state without (100K - 500K) and with (>500K) orbital degeneracy. We attribute the lack of orbital degeneracy up to 500K to (probably local) Jahn-Teller distortions of the CoO$_6$ octahedra. A strong reduction or disappearance of the Jahn-Teller distortions seems to arise from the insulator-to-metal transition around 500 K.
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We study the magnetic susceptibility of mixed-valent La2-xSrxCoO4 single crystals in the doping range of 0.5<= x <= 0.8 for temperatures up to 1000 K. The magnetism below room temperature is described by paramagnetic Co2+ in the high-spin state and by Co3+ in the non-magnetic low-spin state. Above room temperature, an increase in susceptibility compared to the behavior expected from Co2+ is seen, which we attribute to a spin-state transition of Co3+. The susceptibility is analyzed by comparison to full-multiplet calculations for the thermal population of the high- and intermediate-spin states of Co3+.
We present powder and single crystal X-ray diffraction data as evidence for a monoclinic distortion in the low spin (S=0) and intermediate spin state (S=1) of LaCoO3. The alternation of short and long bonds in the ab plane indicates the presence of eg orbital ordering induced by a cooperative Jahn-Teller distortion. We observe an increase of the Jahn-Teller distortion with temperature in agreement with a thermally activated behavior of the Co3+ ions from a low-spin ground state to an intermediate-spin excited state.
We investigate the spin state of LaCoO3 using state-of-the-art photoemission spectroscopy and ab initio band structure calculations. The GGA+U calculations provide a good description of the ground state for the experimentally estimated value of electron correlation strength, U. In addition to the correlation effect, spin-orbit interaction is observed to play a significant role in the case of intermediate spin and high spin configurations. The comparison of the calculated Co 3d and O 2p partial density of states with the experimental valence band spectra indicates that at room temperature, Co has dominant intermediate spin state configuration and that the high spin configuration may not be significant at this temperature. The lineshape of the La 5p and O 2s core level spectra could be reproduced well within these ab initio calculations.
We present magnetization and magnetostriction studies of the insulating perovskite LaCoO3 in magnetic fields approaching 100 T. In marked contrast with expectations from single-ion models, the data reveal two distinct first-order spin transitions and well-defined magnetization plateaux. The magnetization at the higher plateau is only about half the saturation value expected for spin-1 Co3+ ions. These findings strongly suggest collective behavior induced by strong interactions between different electronic -- and therefore spin -- configurations of Co3+ ions. We propose a model of these interactions that predicts crystalline spin textures and a cascade of four magnetic phase transitions at high fields, of which the first two account for the experimental data.
We studied the spin-state responses to light impurity doping in low-spin perovskite LaCoO$_{3}$ (Co^3+: d^6) through magnetization and X-ray fluorescence measurements of single-crystal LaCo$_{0.99}$$M_{0.01}$O$_{3}$ ($M$ = Cr, Mn, Fe, Ni). In the magnetization curves measured at 1.8 K, a change in the spin-state was not observed for Cr, Mn, or Fe doping but was observed for Ni doping. Strong magnetic anisotropy along the [100] easy axis was also found in the Ni-doped sample. The fluorescence measurements revealed that the valences were roughly estimated to be Cr^3+, Mn^4+, Fe^(3+delta)+, and Ni^3+. From the observed chemical trends, we propose that the chemical potential is a key factor in inducing the change of the low-spin state. By expanding a model of the ferromagnetic spin-state heptamer generated by hole doping, we discuss the emergence of highly anisotropic ferromagnetic spin-state clusters induced by low-spin Ni^3+ with Jahn-Teller activity. We also discuss applicability of the present results to mantle materials and impurity-doped pyrites with Fe (d^6).
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