ABSTRACT
Layered vanadium oxides have been extensively explored due to their interesting metal-insulator transitions and energy conversion/storage applications. In the present study, we have successfully synthesized VO2 (A) polymorph powder samples by a single-step hydrothermal synthesis process and consolidated them using spark plasma sintering. The structural and electronic properties of VO2 (A) are measured over a large temperature range from liquid helium, across the structural transition (400-440 K) and up to 500 K. The structural analysis around this transition reveals an antiferrodistorsive to partially ferrodistorsive ordering upon cooling. It is followed by a progressive antiferromagnetic spin pairing which fully settles at about 150 K. The transport measurements show that, in contrast to the rutile archetype VO2 (R/M1), the structural transition comes with a transition from semiconductor to band-type insulator. Under these circumstances, we propose a scenario with a high temperature antiferrodistorsive paramagnetic semiconducting phase, followed by an intermediate regime with a partially ferrodistorsive paramagnetic semiconducting phase, and finally a low temperature partially ferrodistorsive antiferromagnetic band insulator phase with a possible V-V Peierls-type pairing.
ABSTRACT
The temperature dependence of the optical and magnetic properties of CuO were examined by means of hybrid density functional theory calculations. Our work shows that the spin exchange interactions in CuO are neither fully one-dimensional nor fully three-dimensional. The temperature dependence of the optical band gap and the (63)Cu nuclear quadrupole resonance frequency of CuO originate from the combined effect of a strong coupling between the spin order and the electronic structure and the progressive appearance of short-range order with temperature.
ABSTRACT
The olivine-type compounds LiMPO4 (M = Mn, Fe, Co, Ni) consist of MO4 layers made up of corner-sharing MO6 octahedra of high-spin M2+ ions. To gain insight into the magnetic properties of these phosphates, their spin exchange interactions were estimated by spin dimer analysis using tight binding calculations and by electronic band structure analysis using first principles density functional theory calculations. Three spin exchange interactions were found to be important for LiMPO4, namely, the intralayer superexchange J1, the intralayer super-superexchange Jb along the b-direction, and the interlayer super-superexchange J2 along the b-direction. The magnetic ground state of LiMPO4 was determined in terms of these spin exchange interactions by calculating the total spin exchange interaction energy under the classical spin approximation. In the spin lattice of LiMPO4, the two-dimensional antiferromagnetic planes defined by the spin exchange J1 are antiferromagnetically coupled by the spin exchange J2, in agreement with available experimental data.
ABSTRACT
The electronic and structural properties of potassium hexaboride, KB(6), were examined by transport, magnetic susceptibility, EPR, and NMR measurements, temperature-dependent crystal structure determination, and electronic band structure calculations. The valence bands of KB(6) are partially empty, but the electrical resistivity of KB(6) reveals that it is not a normal metal. The magnetic susceptibility as well as EPR and NMR measurements show the presence of localized electrons in KB(6). The EPR spectra of KB(6) have two peaks, a broad ( approximately 320 G) and a narrow (less than approximately 27 G) line width, and the temperature-dependence of the magnetic susceptibility of KB(6) exhibits a strong hysteresis below 70 K. The temperature-dependent crystal structure determination of KB(6) shows the occurrence of an unusual variation in the unit cell parameter hence supporting that the hysteresis of the magnetic susceptibility is a bulk phenomenon. The line width DeltaH(pp) of the broad EPR signal is independent of temperature and EPR frequency. This finding indicates that the line broadening results from the dipole-dipole interaction, and the spins responsible for the broad EPR peak has the average distance of approximately 1.0 nm. To explain these apparently puzzling properties, we examined a probable mechanism of electron localization in KB(6) and its implications.
ABSTRACT
Electrical resistivity, magnetic susceptibility, and electron paramagnetic resonance measurements were carried out for cubic hexaboride KB(6), which is one electron short of completely filling its conduction band. It is found that KB(6) is not metallic and has localized spins. KB(6) exhibits a highly unusual hysteresis in the magnetic susceptibility below 100 K, which suggests that it undergoes a slow relaxation process.
ABSTRACT
The perovskites LaMnO(3) and CaFeO(3) consisting of high-spin d(4) transition metal ions undergo different types of distortions, i.e., a Jahn-Teller distortion in LaMnO(3) and a charge disproportionation in CaFeO(3). We investigated the electronic factor causing this difference on the basis of first principles spin-polarized electronic band structure calculations for their ideal cubic structures and also tight-binding electronic band structure calculations for their ideal cubic and distorted structures. Our study shows that a charge disproportionation is favored over a Jahn-Teller distortion in CaFeO(3) because the covalent character is strong in the Fe-O bond, while the opposite is true for LaMnO(3) because the covalent character is weak in the Mn-O bond. In spin-polarized electronic band structure calculations, the covalency of the M-O (M = Fe, Mn) bond is enhanced in the up-spin bands but is reduced in the down-spin bands. Our analysis shows that electron-electron repulsion causes the energy gap between the metal 3d and the oxygen 2p orbitals to become larger for the down-spin than for the up-spin-orbital interactions. Thus in the d-block e(g) bands of both LaMnO(3) and CaFeO(3) the metal 3d orbital contribution is larger in the down-spin than in the up-spin bands.
