ABSTRACT
Zircon-type NdVO4and scheelite-type PrVO4have been studied by means of Raman spectroscopy up to approximately 20 GPa. In the first compound, zircon-scheelite and scheelite-fergusonite phase transitions are reported at 6.4(3) and 19.6(4) GPa, respectively. In the case of scheelite-type PrVO4, a reversible phase transition to a PbWO4-III structure is observed at 16.8(5) GPa. In both cases, a scheelite-type structure is recovered in a metastable state at low pressures. The pressure evolution of the Raman modes is also reported. Our experimental findings are supported byab initiocalculations, which allowed us to discuss the role of mechanic and dynamical instabilities in the phase transition mechanisms.
ABSTRACT
The intriguing coupling phenomena among spin, phonon, and charge degrees of freedom in materials having magnetic, ferroelectric and/or ferroelastic order have been of research interest for the fundamental understanding and technological relevance. We report a detailed study on structure and phonons of Al0.5Ga0.5FeO3 (ALGF), a lead-free magnetoelectric material, carried out using variable temperature dependent powder neutron diffraction and Raman spectroscopy. Neutron diffraction studies suggest that Al3+ ions are distributed in one tetrahedrally (BO4) and three octahedrally (BO6) coordinated sites of the orthorhombic (Pc21n) structure and there is no structural transition in the temperature range of 7-800 K. Temperature dependent field-cooled and zero-field-cooled magnetization studies indicate ferrimagnetic ordering below 225 K (TN), and that is reflected in the low temperature powder neutron diffraction data. An antiferromagnetic type arrangement of Fe3+ ions with net magnetic moment of 0.13 µB/Fe3+ was observed from powder neutron diffraction analysis and it corroborates the findings from magnetization studies. At the magnetic transition temperature, no drastic change in lattice strain was observed, while significant changes in phonons were observed in the Raman spectra. The deviation of several mode frequencies from the standard anharmonicity model in the ferrimagnetic phase (below 240 K) is attributed to coupling effect between spin and phonon. Spin-phonon coupling effect is discernable from Raman bands located at 270, 425, 582, 695, 738, and 841 cm-1. Their coupling strengths (λ) have been estimated using our phonon spectra and magnetization results. BOn (n = 4, 6) libration (restricted rotation) mode at 270 cm-1 has the largest coupling constant (λâ¼ 2.3), while the stretching vibrations located at 695 and 738 cm-1 have the lowest coupling constant (λâ¼ 0.5). In addition to the libration mode, several internal stretching and bending modes of polyhedral units are strongly affected by spin ordering.
ABSTRACT
Monazite-type BiPO4, LaPO4, CePO4, and PrPO4 have been studied under high pressure by ab initio simulations and Raman spectroscopy measurements in the pressure range of stability of the monazite structure. A good agreement between experimental and theoretical Raman-active mode frequencies and pressure coefficients has been found which has allowed us to discuss the nature of the Raman-active modes. Besides, calculations have provided us with information on how the crystal structure is modified by pressure. This information has allowed us to determine the equation of state and the isothermal compressibility tensor of the four studied compounds. In addition, the information obtained on the polyhedral compressibility has been used to explain the anisotropic axial compressibility and the bulk compressibility of monazite phosphates. Finally, we have carried out a systematic discussion on the high-pressure behavior of the four studied phosphates in comparison to results of previous studies.
ABSTRACT
This work reports the structural and vibrational properties of nanocrystals of corundum-type In2O3 (rh-In2O3) at high pressures by using angle-dispersive x-ray diffraction and Raman scattering measurements up to 30 GPa. The equation of state and the pressure dependence of the Raman-active modes of the corundum phase in nanocrystals are in good agreement with previous studies on bulk material and theoretical simulations on bulk rh-In2O3. Nanocrystalline rh-In2O3 showed stability under compression at least up to 20 GPa, unlike bulk rh-In2O3 which gradually transforms to the orthorhombic Pbca (Rh2O3-III-type) structure above 12-14 GPa. The different stability range found in nanocrystalline and bulk corundum-type In2O3 is discussed.
ABSTRACT
We report composition dependent structure evolution from SrTiO3 to SrFe0.5Ta0.5O3 by powder X-ray and neutron diffraction studies of SrTi1-2xFexTaxO3 (0.00 ≤ × ≤ 0.50) compositions. Structural studies reveal cubic (Pm3m) perovskite-type structure of the parent SrTiO3 for x up to 0.075 and cation disordered orthorhombic (Pbnm) perovskite-type structure for x ≥ 0.33. A biphasic region consisting of a mixture of cubic and orthorhombic structures is found in the range for 0.10 ≤ × ≤ 0.25. Dielectric studies reveal transformation from a normal dielectric to relaxor like properties with increasing Fe(3+) and Ta(5+) concentration. Dielectric response is maximum at x = 0.33 in the series. The results establish a protocol for designing new lead-free relaxor materials based on the co-substitution of Fe(3+) and Ta(5+) for Ti(4+) in SrTiO3. A complex interplay of strain effects arising from distribution of cations at the octahedral sites of the perovskite structure controls the dielectric properties.
ABSTRACT
The compression behavior of zircon-type samarium orthovanadate, SmVO4, has been investigated using synchrotron-based powder x-ray diffraction and ab initio calculations of up to 21 GPa. The results indicate the instability of ambient zircon phase at around 6 GPa, which transforms to a high-density scheelite-type phase. The high-pressure phase remains stable up to 21 GPa, the highest pressure reached in the present investigations. On pressure release, the scheelite phase is recovered. The crystal structure of the high-pressure phase and the equations of state for the zircon- and scheelite-type phases have been determined. Various compressibilities, such as the bulk, axial and bond compressibilities, estimated from the experimental data are found to be in good agreement with the results obtained from theoretical calculations. The calculated elastic constants show that the zircon structure becomes mechanically unstable beyond the transition pressure. Overall there is good agreement between the experimental and theoretical findings.
ABSTRACT
A titania mineral (obtained from East coast, Orissa, India) was investigated by X-ray diffraction (XRD), photoacoustic spectroscopy (PAS), Raman and Electron Paramagnetic Resonance (EPR) studies. XRD studies indicated the presence of rutile (91%) and anatase (9%) phases in the mineral. Raman investigation supported this information. Both rutile and anatase phases have tetragonal structure (rutile: space group P4(2)/mnm, a=4.5946(1) Å, c=2.9597(1) Å, V=62.48(1) (Å)(3), Z=2; anatase: space group I4(1)/amd, 3.7848(2) Å, 9.5098(11) Å, V=136.22(2) (Å)(3), Z=4). The deconvoluted PAS spectrum showed nine peaks around 335, 370, 415,485, 555, 605, 659, 690,730 and 785 nm and according to the ligand field theory, these peaks were attributed to the presence of V(4+), Cr(3+), Mn(4+) and Fe(3+) species. EPR studies revealed the presence of transition metal ions V(4+)(d(1)), Cr(3+)(d(3)), Mn(4+)(d(3)) and Fe(3+)(d(5)) at Ti(4+) sites. The EPR spectra are characterized by very large crystal filed splitting (D term) and orthorhombic distortion term (E term) for multiple electron system (s>1) suggesting that the transition metal ions substitute the Ti(4+) in the lattice which is situated in distorted octahedral coordination of oxygen. The possible reasons for observation of unusually large D and E term in the EPR spectra of transition metal ions (S=3/2 and 5/2) are discussed.
Subject(s)
Spectrum Analysis/methods , Titanium/chemistry , Chromium/chemistry , Electron Spin Resonance Spectroscopy , India , Iron/chemistry , Manganese/chemistry , Minerals/chemistry , Spectrum Analysis, Raman , Vanadium/chemistry , X-Ray DiffractionABSTRACT
In this work we report the metastability and the energetics of the phase transitions of three different polymorphs of BiPO4, namely trigonal (Phase-I, space group P3(1)21), monoclinic monazite-type (Phase-II, space group P2(1)/n) and SbPO4-type monoclinic (Phase-III, space group P2(1)/m) from ambient and non-ambient temperature powder XRD and neutron diffraction studies as well as ab initio density functional theory (DFT) calculations. The symmetry ambiguity between P2(1) and P2(1)/m of the high temperature polymorph of BiPO4 has been resolved by a neutron diffraction study. The structure and vibrational properties of these polymorphs of the three polymorphs have also been reported in detail. Total energy calculations have been used to understand the experimentally observed metastable behavior of trigonal and monazite-type BiPO4. Interestingly, all of the three phases were found to coexist after heating a single phasic trigonal BiPO4 to 773 K. The irreversible nature of these phase transitions has been explained by the concepts of the interplay of the structural distortion, molar volume and total energy.
ABSTRACT
Recently colossal volume thermal expansion has been observed in the framework compounds Ag(3)Co(CN)(6) and Ag(3)Fe(CN)(6). We have measured phonon spectra using neutron time-of-flight spectroscopy as a function of temperature and pressure. Ab initio calculations were carried out for the sake of analysis and interpretation. Bonding is found to be very similar in the two compounds. At ambient pressure, modes in the intermediate frequency part of the vibrational spectra in the Co compound are shifted slightly to higher energies as compared to the Fe compound. The temperature dependence of the phonon spectra gives evidence for a large explicit anharmonic contribution to the total anharmonicity for low-energy modes below 5 meV. We have found that modes are mainly affected by the change in size of the unit cell, which in turn changes the bond lengths and vibrational frequencies. Thermal expansion has been calculated via the volume dependence of phonon spectra. Our analysis indicates that Ag phonon modes within the energy range 2-5 meV are strongly anharmonic and major contributors to thermal expansion in both systems. The application of pressure hardens the low-energy part of the phonon spectra involving Ag vibrations and confirms the highly anharmonic nature of these modes.
ABSTRACT
A series of samples with composition Gd(2-y)Ce(y)Zr(2)O(7) (0.0 ≤ y ≤ 2.0) were prepared by the gel combustion method followed by high-temperature reduction. The details of the structural variations as a function of the composition, temperature, and oxygen stoichiometry have been investigated by X-ray diffraction (XRD), high-temperature XRD (HT-XRD), and thermogravimetry. A complete solubility of Gd(3+) in Ce(2)Zr(2)O(7) and Ce(2)Zr(2)O(8) could be achieved by this adaptive preparative method. Analysis of the XRD data revealed a sequential variation of the structural features with oxygen stoichiometry as well as Gd(3+) contents in these compositions. The variation in the unit cell parameter along the compositions has a strong influence on the oxygen uptake behavior in the Gd(2-y)Ce(y)Zr(2)O(7) system, as observed from the thermogravimetric and HT-XRD studies. The preparation and stability of various metastable phases in Gd-Ce-Zr-O have been addressed in detail. The details of the study will be useful for the design and application of a potential redox catalyst and an oxygen storage capacitor.
ABSTRACT
We present the structural and magnetic properties of Zn(0.95-x)Co(0.05)Al(x)O (x = 0.0 to 0.1) nanoparticles, synthesized by a novel sol-gel route followed by pyrolysis. Powder X-ray diffraction data confirms the formation of a single phase wurtzite type ZnO structure for all the compositions. The Zn(0.95)Co(0.05)O nanoparticles show diamagnetic behavior at room temperature. However, when Al is co-doped with Co with x = 0.0 to 0.10 in Zn(0.95-x)Co(0.05)Al(x)O, a systematic increase in ferromagnetic moment is observed up to x = 0.07 at 300 K. Above x = 0.07 (e.g. for x = 0.10) a drastic decrease in ferromagnetic nature is observed which is concomitant with the segregation of poorly crystalline Al rich ZnO phase as evidenced from TEM studies. Theoretical studies using density functional calculations on Zn(0.95-x)Co(0.05)Al(x)O suggest that the partial occupancy of S2 states leads to an increased double exchange interaction favoring the ferromagnetic ground states. Such ferromagnetic interactions are favorable beyond a threshold limit. At a high level doping of Al, the exchange splitting is reduced, which suppresses the ferromagnetic ordering.
