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Sr1 − x Ca x Mn0.5Ti0.5O3 (x = 0.25, 0.5 and 0.75) polycrystalline samples were synthesized by conventional solid-state reaction. Magnetic characterizations of Sr1 − x Ca x Mn0.5Ti0.5O3 revealed signature of antiferromagnetic ordering at temperatures (T N) ~19, 25 and 29.5 K for x = 0.25, x = 0.5 and for x = 0.75, respectively. Sr1 − x Ca x Mn0.5Ti0.5O3 (x = 0.75) exhibits field-induced antiferromagnetic to ferromagnetic transition at ~30 K with applied magnetic field of 4 and 5 T. Magnetocaloric change (ΔS M) increases from 3.5 to 19 J/kg K by increasing calcium concentration in the A-site. Those ΔS M values are relatively very high in these classes of antiferromagnetic perovskite systems and equal to the magnetisation values of the ferromagnetic perovskite manganites. This is the first report for the Sr1 − x Ca x Mn0.5Ti0.5O3 (x = 0.75) having large magnetic entropy changes induced by the low magnetic field.

First-principle calculations based on density functional theory have been performed to investigate the negative electrode behaviors, structural changes, and electronic and bonding properties of lithium intercalated antimonides Ag3Sb and Mg3Sb2. Initial intercalation of lithium to orthorhombic Ag3Sb led to form cubic Li2AgSb. Lithium insertion to hexagonal Mg3Sb2 results in cubic LiMgSb. Further insertion of lithium with the intercalated compounds Li2AgSb and LiMgSb results in to the formation of alkali antimonide Li3Sb. The structural transformation of both antimonides Ag3Sb and Mg3Sb2 followed by the insertion of Li+ ends with the formation of Li3Sb with cubic phase. The computed band structures along high symmetry directions of the Brillouin zone, and total and partial density of states clearly illustrate that the intercalation of lithium with Ag3Sb and Mg3Sb2 changes their metallic nature into semiconductor. From the charge density calculations, it is observed that the covalent bond nature in the parent phases Ag3Sb and Mg3Sb2 changed into ionic bond in the Li+ intercalated phases Li2AgSb, LiMgSb, and Li3Sb.

The oxygen-deficient strontium iron oxide SrFeO3−δ (SFO) exhibits richness in the phase diagram over a broad range of temperatures and for other external parameters. Room-temperature X-ray diffraction and Raman spectrum reveals that the structure of synthesized SFO system consists of two mixed phases, i.e., major orthorhombic and minor tetragonal phases. The low-temperature Raman and vibrating sample magnetometer measurements indicated a structural transition below 253 K. The magnetic property of the synthesized SFO for various external magnetic field (up to 5 T) reveals possible variation in oxygen stoichiometry. Also, the application of external H increases Neel transition temperature (T N), suppresses the hysteresis width (W H), and thus weakens the first-order nature of the transition. Our analysis revealed the vanishing of hysteresis and the first-order antiferromagnetic transition becomes a crossover above a critical magnetic field H CR ≈ 5 T. Possible switching of magnetic ordering and oxidation state observed in same system enhances interest in related compounds which may be used in magnetic sensors and other magnetic switching devices.

First principle calculations based on density functional theory have been performed on lithium containing transition metal sulfides Li2TiS3 and Li3NbS4 which are recently identified as novel positive electrode materials for rechargeable Li+ batteries. The calculations were performed to investigate the structural stability, electronic and transport properties of Li2TiS3 and Li3NbS4 along with their corresponding delithiated phases LiTiS3 and Li2NbS4. In this study it has been observed that these lithium containing sulfur materials maintain their face-centered cubic structure upon extraction of Li+. To calculate the structural stability and volume change due to lithium extraction, the total energies of Li2TiS3, Li3NbS4 and their corresponding delithiated phases LiTiS3 and Li2NbS4 have been computed by applying full potential linearized augmented plane wave (FP-LAPW) method implemented in WIEN2K. The equilibrium structural parameters for all the phases were determined by achieving total energy convergence. These electrode materials exhibit very small percentage of volume change with change in Li+ concentration which accounts for excellent structural stability. The computed band structure along high symmetry lines in the Brillouin zone, total and partial density of states clearly reveals that the extraction lithium from these electrode materials does not change their metallic nature. The electronic conductivities of both lithiated and delithiated phases have been calculated by employing BoltzTrap which can be interfaced with WIEN2K. The topological distributions of electron charge density at various critical points within the system were analyzed with the use of CRITIC code which is based on Bader’s theory of atoms in molecules (AIM). From the charge density calculations, it was observed that, there is strong ionic bond and weak covalent bond between atoms of the compounds Li2TiS3 and Li3NbS4. But the ionic bond nature was found to decrease in the delithiated phases LiTiS3 and Li2NbS4. The calculated values of electronic conductivities and discharge voltages for both electrodes are found to be in accordance with the recent experimental reports.

The transport phenomena in alkali-metal super ionic conductors based on Na3PO4 structure are of particular interest due to their potential technological application. Differential thermal analysis (DTA), differential scanning calorimetry (DSC), Raman spectroscopy and temperature dependent electrical conductivity measurements were carried out to probe the nature of the phase transformation involved in anhydrous Na3PO4. The changes in spectral profile of the v3 mode and the line width of v1 mode of PO 4 3− observed in the temperature interval from 331 to 345 °C revealed the high degree of disorder nature during the α-γNa3PO4 phase transformation.

The understanding of molecular level structural information of phosphate glasses is very much essential. The unique microwave-absorbing ability of NaH2PO4·2H2O was found to be very useful for preparing crystal and glassy sodium super ionic conductors (Nasicon's) as a component of batch mixtures. In this work NaPO3 glass was prepared by both conventional melt quench and microwave heating from NaH2PO4·2H2O as a starting material. The structure of NaPO3 glass and their structural evolution upon heating through glass transition were probed by combination of complementary techniques like differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) and thermo-Raman spectroscopy.

The electronic band structure and the total energy of SrX (X=S, Se, Te) in NaCl-type and CsCl-type structures were studied using the tight binding linear muffin-tin orbital method. The calculated ground state properties such as lattice constant and bulk modulus are in agreement with the experimental values. The transition pressures and volumes also agree well with the experimental results. The energy gap at ambient conditions were calculated. The metallization pressures and volumes have also been estimated.