No Arabic abstract
The effect of rare-earth ion size on the octahedral distortions in rare-earth chromites (RCrO3, R = Lu, Tb, Gd, Eu, Sm) crystallizing in the orthorhombic structure has been studied using Raman scattering and synchrotron powder x-ray diffraction up to 20 GPa. From our studies on RCrO3 we found that the octahedral tilts (distortions) increase with pressure. This is contrary to the earlier report which suggests that in LaCrO3, the distortions decrease with pressure leading to a more ordered phase at high pressure. Here we observe that the rate of increase in distortion decreases with the increase in R-ion radii. This occurs due to the reduction in the compression of RO12 polyhedra with a corresponding increase in the compression of the CrO6 octahedra with increasing R-ion radii. From the Raman studies, we predict a critical R-ion radii, above which we expect the distortions in RCrO3 to reduce with increasing pressure leading to what is observed in the case of LaCrO3. These Raman results are consistent with our pressure dependent structural studies on RCrO3 (R = Gd, Eu, Sm). Also, our results suggest that the pressure dependence of Neel temperature, TNCr, (where the Cr3+ spin orders) in RCrO3 is mostly affected by the compressions of Cr-O bonds rather than the alteration of octahedral tilts.
We report a Raman scattering study of six rare earth orthoferrites RFeO3, with R = La, Sm, Eu, Gd, Tb, Dy. The use of extensive polarized Raman scattering of SmFeO3 and first-principles calculations enable the assignment of the observed phonon modes to vibrational symmetries and atomic displacements. The assignment of the spectra and their comparison throughout the whole series allows correlating the phonon modes with the orthorhombic structural distortions of RFeO3 perovskites. In particular, the positions of two specific Ag modes scale linearly with the two FeO6 octahedra tilt angles, allowing the distortion throughout the series. At variance with literature, we find that the two octahedra tilt angles scale differently with the vibration frequencies of their respective Ag modes. This behavior as well as the general relations between the tilt angles, the frequencies of the associated modes and the ionic radii are rationalized in a simple Landau model. The reported Raman spectra and associated phonon-mode assignment provide reference data for structural investigations of the whole series of orthoferrites.
We report on electronic collective excitations in RMn2O5 (R= Pr, Sm, Gd, Tb) showing condensation starting at and below TNsimTCsim40-50 K. Its origin is understood as partial delocalized eg electron orbitals in the Jahn-Teller distortion of the pyramids dimmer with strong hybridized Mn3+-O bonds. Our local probes, Raman, infrared, and X-ray absorption, back the conclusion by which there is no structural phase transition at TNsimTC. Ferroelectricity is magnetically assisted by electron localization triggering lattice polarizability by unscreening. We have also found phonon hardening as the rare earth is sequentially replaced. This is understood as consequence of lanthanide contraction. It is suggested that partially f-electron screened Rare Earth nuclei might be introducing a perturbation to eg electrons prone to delocalize as the superexchange interaction takes place.
We have studied the thermal conductivity $kappa$ on single crystalline samples of the antiferromagnetic monolayer cuprates R$_2$CuO$_4$ with R = La, Pr, Nd, Sm, Eu, and Gd. For a heat current within the CuO$_2$ planes, i.e. for $kappa_{ab}$ we find high-temperature anomalies around 250 K in all samples. In contrast, the thermal conductivity $kappa_c$ perpendicular to the CuO$_2$ planes, which we measured for R = La, Pr, and Gd, shows a conventional temperature dependence as expected for a purely phononic thermal conductivity. This qualitative anisotropy of $kappa_i$ and the anomalous temperature dependence of $kappa_{ab}$ give evidence for a significant magnetic contribution $kappa_{mag}$ to the heat transport within the CuO$_2$ planes. Our results suggest, that a large magnetic contribution to the heat current is a common feature of single-layer cuprates. We find that $kappa_{mag}$ is hardly affected by structural instabilities, whereas already weak charge carrier doping causes a strong suppression of $kappa_{mag}$.
The time-differential perturbed-angular-correlation (TDPAC) technique was applied to the study of the internal electric-field gradient (EFG) in Eu- and Ho-sesquioxides in their cubic bixbyite phases. The results, as well as previous characterizations of the EFG at $^{181}$Ta sites in oxides with the bixbyite structure, were compared to those obtained in experiments using $^{111}$Cd as probe, and to point-charge model and {it ab initio} results calculations for the EFG tensor at impurity sites in binary oxides. These studies provide quantitative information about electronic processes and the structural relaxations induced by the presence of impurity probes in the host lattices, and confirm the existence of nonionic contributions to the EFG in these systems. Our FP-LAPW calculations show that this nonionic contribution to the EFG is the dominating one, and that it is originated in the population of {it p} states (5{it p} in the case of Cd, 6{it p} for Ta).
We performed femtosecond reflection spectroscopy on a series of perovskite-type cobalt oxide $R$BaCo$_2$O$_{6-delta}$ ($R$=Sm, Gd, and Tb) crystals, in which the electronic transfer was controlled by $R$. The transient reflectivity and the optical conductivity ($sigma^{rm PI}(omega)$) obtained by Kramers-Kronig analysis showed an ultrafast change within a time resolution ($approx 150$ fs) at room temperature and the appearance of signals of a hidden state different from the high temperature metallic state. The transferred spectral weight in $sigma^{rm PI}(omega)$ upon photoexcitation sensitively depended on the $R$-species, indicating an important role of electronic correlation in the photoexcited state.