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Register a new userShort-Range Structure and Phonon Assignment of the Brownmillerite-Type Oxide Ba$_{2}$In$_{2}$O$_{5}$ and its Hydrated Proton-Conducting Form BaInO$_{3}$H
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The vibrational spectra and short-range structure of the brownmillerite-type oxide Ba$_{2}$In$_{2}$O$_{5}$ and its hydrated form BaInO$_{3}$H, are investigated by means of Raman, infrared, and inelastic neutron scattering spectroscopies together with density functional theory calculations. For Ba$_{2}$In$_{2}$O$_{5}$, which may be described as an oxygen deficient perovskite structure with alternating layers of InO$_{6}$ octahedra and InO$_{4}$ tetrahedra, the results affirm a short-range structure of $Icmm$ symmetry, which is characterized by random orientation of successive layers of InO$_{4}$ tetrahedra. For the hydrated, proton conducting, form, BaInO$_{3}$H, the results suggest that the short-range structure is more complicated than the $P4/mbm$ symmetry that has been proposed previously on the basis of neutron diffraction, but rather suggest a proton configuration close to the lowest energy structure predicted by Martinez et al. [J.-R. Martinez, C. E. Moen, S. Stoelen, N. L. Allan, J. of Solid State Chem. 180, 3388, (2007)]. An intense Raman active vibration at 150 cm$^{-1}$ is identified as a unique fingerprint of this proton configuration.
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The structure and dehydration mechanism of the proton conducting oxide Ba$_{2}$In$_{2}$O$_{5}$(H$_{2}$O)$_{x}$ are investigated by means of variable temperature Raman spectroscopy together with inelastic neutron scattering. At room temperature, Ba$_{2}$In$_{2}$O$_{5}$(H$_{2}$O)$_{x}$ is found to be fully hydrated ($x=1$) and to have a perovskite-like structure, which dehydrates gradually with increasing temperature and at around 600 $^{circ}$C the material is essentially completely dehydrated ($x=0$). The dehydrated material exhibits a brownmillerite structure, which is featured by alternating layers of InO$_{6}$ octahedra and InO$_{4}$ tetrahedra. The transition from a perovskite-like to a brownmillerite-like structure is featured by a hydrated-to-intermediate phase transition at $ca.$ 370 {deg}C. The structure of the intermediate phase is similar to the structure of the fully dehydrated material, but with the difference that it exhibits a non-centrosymmetric distortion of the InO$_{6}$ octahedra not present in the latter. For temperatures below the hydrated-to-intermediate phase transition, dehydration is featured by the release of protons confined to the layers of InO$_{4}$ tetrahedra, whereas above the transition also protons bound to oxygens of the layers of InO$_{6}$ are released. Finally, we found that the O-H stretch region of the vibrational spectra is not consistent with a single-phase spectrum, but is in agreement with the superposition of spectra associated with two different proton configurations. The relative contributions of the two proton configurations depend on how the sample is hydrated.
In a systematic study we investigate the effect of dopant level and hydration on the short-range structure of the proton conducting perovskite-type oxide BaIn_{x}Zr_{1-x}O_{3-x/2} (x = 0-0.75), using infrared and Raman spectroscopy. The results show that doping leads to significant local distortions of the average cubic structure of these materials. By increasing the In concentration from x = 0 to x = 0.75 new bands appear and grow in intensity in both the IR and Raman spectra, showing that the local distortions become successively more and more pronounced. The structural distortions are largely uncorrelated to the presence of oxygen vacancies, but instead are mainly driven by the size difference between the In^{3+} and Zr^{4+} ions, which leads to displacements of the cations and to tilting of the (In/Zr)O_{6} octahedra. Based on our results, we suggest that there is a threshold between x = 0.10 and x = 0.25 where the local structural distortions propagate throughout the whole perovskite structure. Comparison of our spectroscopic data with the proton conductivity reported for the same materials indicates that the presence of extended structural distortions are favorable for fast proton transport.
PbFe$_{1/2}$Ta$_{1/2}$O$_{3}$ (PFT) belongs to the family of PbB$_{x}$B$_{1-x}$O$_{3}$ which have inherent chemical disorder at the B-site. Due to this disorder, a complex magnetic phase diagram is expected in the material. In this paper, we report experimental results of magnetic properties in PFT through macroscopic characterization, neutron scattering and M{o}ssbauer spectroscopy techniques. With these results we show for the first time that PbFe$_{1/2}$Ta$_{1/2}$O$_{3}$ behaves very similar to PbFe$_{1/2}$Nb$_{1/2}$O$_{3}$, i.e, it undergoes AF transition at 153 K and has a spinglass transition at 10 K, below which the antiferromagnetism coexists with spinglass. We suggest that the mechanism which is responsible for such a non-trivial ground state can be explained by a speromagnet-like spin arrangement similar to the one proposed for PbFe$_{1/2}$Nb$_{1/2}$O$_{3}$.
Ba$_{3}$NbFe$_{3}$Si$_{2}$O$_{14}$ (langasite) is structurally and magnetically single domain chiral with the magnetic helicity induced through competing symmetric exchange interactions. Using neutron scattering, we show that the spin-waves in antiferromagnetic langasite display directional anisotropy. On applying a time reversal symmetry breaking magnetic field along the $c$-axis, the spin wave energies differ when the sign is reversed for either the momentum transfer $pm$ $vec{Q}$ or applied magnetic field $pm$ $mu_{0}$H. When the field is applied within the crystallographic $ab$-plane, the spin wave dispersion is directionally textit{isotropic} and symmetric in $pm$ $mu_{0}$H. However, a directional anisotropy is observed in the spin wave intensity. We discuss this directional anisotropy in the dispersion in langasite in terms of a field induced precession of the dynamic unit cell staggered magnetization. Directional anisotropy, or often referred to as non reciprocal responses, can occur in antiferromagnetic phases in the absence of the Dzyaloshinskii-Moriya interaction or other effects resulting from spin-orbit coupling.
Erythrosiderites with the formula A2FeX5H2O, where A = Rb, K, and (NH4) and X = Cl and Br are intriguing systems that possess various magnetic and electric phases, as well as multiferroic phases in which magnetism and ferroelectricity are coupled. In this report, we study the magnetic phase diagram of erythrosiderites as a function of superexchange interactions. To this end, we perform classical Monte Carlo simulations on magnetic Hamiltonians that contain five different superexchange interactions with single-ion anisotropies. Our phase diagram contains all magnetic ground states that have been experimentally observed in these materials. We argue that the ground states can be explained by varying the ratio of J4/J2. For J4/J2 > 0.95 a cycloidal spins structure is stabilized as observed in (NH4)2FeCl5H2O and otherwise, a collinear spin structure is stabilized as observed in (K,Rb)2FeCl5H2O. We also show that the difference in the single-ion anisotropy along a- and c- axes is essential to stabilize the intermediate state observed in (NH)2FeCl5H2O.
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