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Pb2Sc2Si2O9 and Pb2In2Si2O9, respectively, the scandium and indium containing structural analogues of the mineral kentrolite are grown by spontaneous crystallization from a PbO flux. The corresponding polycrystalline powder samples are synthesized by conventional solid-state approach. The compounds are thoroughly characterized using temperature-dependent single crystal and powder X-ray diffraction, heat capacity measurements, second harmonic generation experiments and Raman spectroscopy. At ambient conditions, both compounds crystallize in the non-centrosymmetric Pna21 space group and undergo phase transitions to the centrosymmetric Pbcn space group at elevated temperatures. The Pbcn into Pna21 phase transitions are complemented by the signals of the temperature-dependent second harmonic generation. The specific heat capacity exhibits distinct cusp, supporting the λ-type second-order phase transition. The temperature dependency of some selective Raman modes further complements the findings, showing softening and hardening of the phonons across the phase transitions. [ABSTRACT FROM AUTHOR]

Pb2Sc2Si2O9 and Pb2In2Si2O9, respectively, the scandium and indium containing structural analogues of the mineral kentrolite are grown by spontaneous crystallization from a PbO flux. The corresponding polycrystalline powder samples are synthesized by conventional solid-state approach. The compounds are thoroughly characterized using temperature-dependent single crystal and powder X-ray diffraction, heat capacity measurements, second harmonic generation experiments and Raman spectroscopy. At ambient conditions, both compounds crystallize in the non-centrosymmetric Pna21 space group and undergo phase transitions to the centrosymmetric Pbcn space group at elevated temperatures. The Pbcn into Pna21 phase transitions are complemented by the signals of the temperature-dependent second harmonic generation. The specific heat capacity exhibits distinct cusp, supporting the λ-type second-order phase transition. The temperature dependency of some selective Raman modes further complements the findings, showing softening and hardening of the phonons across the phase transitions. [ABSTRACT FROM AUTHOR]

Summary: Within first principles calculations, the electronic structure, thermodynamic, mechanical stability, magnetism, and phonon properties of the inverse perovskite (Na3OCl) have been summed up. The Birch‐Murnaghan derived lattice constant and bond‐lengths are identical, when compared to the experimental data. A direct energy gap of 2.18 eV observed from the band structure reveals the semiconducting nature of the present oxide. Also, the application of strain on electronic properties predicts the decrease in bandgap with respect to compressive strain and vice versa. The constituent nonmagnetic atoms in its crystal propose the total magnetic moment to be zero and the same is supported by susceptibility data. In addition to the negative Cauchy's pressure, the small bulk modulus compared to Young's modulus determined from elastic constants, possibly claims it as a brittle material. Also, the temperature dependent Gruneisen parameter (1.58) and Debye temperature (382.27 K) are determined to reveal the lattice thermal conductivity (κ = 6.48 W/mK) at room temperature. [ABSTRACT FROM AUTHOR]

This study presents an investigation on the axial negative thermal expansion of α-PbAlBO4 and β-PbAlBO4. Polycrystalline and single-crystal samples were prepared by solid-state synthesis method, characterized by temperature- and pressure-dependent X-ray and neutron diffraction experiments. The axial negative linear compressibility (NLC) is known for the α-polymorph, although structurally different the β-polymorph also shows similar NLC phenomenon. The lattice thermal expansion was described using the first-order Grüneisen equation of state, where the vibrational energy was calculated using the Debye–Einstein-Anharmonicity model. The density functional theory (DFT)-based phonon density of states and Raman spectra helped to choose the characteristic frequency to model the metric parameters. Lattice thermal expansion was additionally simulated in the quasi-harmonic approximation using the plane-wave DFT approach at the PBEsol level. The apparent departure of the quasi-harmonic approximation model has been discussed in terms of associated thermodynamic functions. The interplay between the topology-induced negative cross-compliance and anisotropic Grüneisen parameter has been identified as the driving force for the axial negative linear compressibility and axial negative thermal expansion. [ABSTRACT FROM AUTHOR]

Novel Pb7O6Br2 (1) lead oxybromide was prepared from Pb oxybromide melt by the "rapid quenching" route. Bonding scheme, thermal expansion, and structural properties were studied. The structural features of this unexpectedly complex phase are described on the basis of lone electron pair stereochemical activity and Pb-Br versus Pb-O bonding scheme. The structure of 1 contains a number of cavities, which can be assigned to the self-containments of the lone electron pairs on Pb2+ cations. "Empty" Pb4 chains are observed in between of the folding sides of the adjacent strongly corrugated oxocentered [Pb7O6]2+ layers. Highly isotropic thermal expansion of 1 appeared to be unexpected. The possible explanations of such a behavior in 1 are given. The structure of 1 is an interesting example of tetrahedral framework with mixed chemical bonding and is the densest known among Pb oxyhalides with the density of 18.4 tetrahedra/1000 ų. Current study shows that oxocentered layers derivatives from α-PbO can be very flexible and form rather dense three-dimensional structural topologies. The properties and structure are compared to other phases crystallizing in the anhydrous PbO-PbX2 (X = F, Cl, Br, I) systems, illustrate the complexity of lead oxyhalides, and reveal new and general pathways for the targeted synthesis of new phases with the Pb-O units of desired dimensionality. The indirect gap value of ~2.04 eV obtained from generalized gradient approximation calculations demonstrates potentially good photocatalytic properties of 1. [ABSTRACT FROM AUTHOR]

Single crystals of the new compound Pb7O6Br2 are prepared by solid state reaction of PbBr2 and α-PbO (Pt crucible, 750 °C, 1 h). [ABSTRACT FROM AUTHOR]

Bismuth ferrites, specifically perovskite-type BiFeO 3 and mullite-type Bi 2 Fe 4 O 9 , hold significant technological promise as catalysts, photovoltaics, and room-temperature multiferroics. However, challenges arise due to their frequent cocrystallization, particularly in the nanoregime, hindering the production of phase-pure materials. This study unveils a controlled sol-gel crystallization approach, elucidating the phase formation complexities in the bismuth ferrite oxide system by coupling thermochemical analysis and total scattering with pair distribution function analysis. We tune the crystallization pathways in the BiFeO 3 -Bi 2 Fe 4 O 9 system by adjusting the metal to complexing agent ratio and pH during precursor preparation with a fixed Bi/Fe ratio of 1:2. Although all precursors undergo an amorphization process during heating, our results demonstrate a consistent correlation between the crystallization pathway and the initial structural entities formed during gel formation. Pair distribution function analysis reveals structural differences in the intermediate amorphous structures, which preferentially crystallize into either BiFeO 3 or Bi 2 Fe 4 O 9 . This study offers mechanistic insights into the formation processes in the system and synthetic guidance for the controlled synthesis of pure Bi 2 Fe 4 O 9 and mixed BiFeO 3 /Bi 2 Fe 4 O 9 nanomaterials. Additionally, it elucidates the unusual growth behavior and structural size dependence of Bi 2 Fe 4 O 9 , particularly highlighting significant distortions in the local structure likely induced by the proximity of Bi's stereoactive lone electron pairs at small sizes., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)