The previously proposed theoretical and experimental structures, bond characterization, and compressibility of Mg（BH4）2 in a pressure range from 0 to 10 GPa are studied by ab initio density-functional calculations. It is found that the ambient pressure phases of meta-stable I41/amd and unstable P-3ml proposed recently are extra stable and cannot decompose under high pressure. Enthalpy calculation indicates that the ground state of F222 structure proposed by Zhou et al. [2009 Phys. Rev. B 79 212102] will transfer to I41/amd at 0.7 GPa, and then to a P-3ml structure at 6.3 GPa. The experimental P6122 structure （a-phase） transfers to I41/amd at 1.2 GPa. Furthermore, both I41/arnd and P-3ml can exist as high volumetric hydrogen density phases at low pressure. Their theoretical volumetric hydrogen densities reach 146.351 g H2/L and 134.028 g H2/L at ambient pressure, respectively. The calculated phonon dispersion curve shows that the I41/amd phase is dynamically stable in a pressure range from 0 to 4 CPa and the P-3ral phase is stable at pressures higher than 1 GPa. So the I41/arnd phase may be synthesized under high pressure and retained to ambient pressure. Energy band structures show that they are both always ionic crystalline and insulating with a band-gap of about 5 eV in this pressure range. In addition, they each have an anisotropic compressibility. The c axis of these structures is easy to compress. Especially, the c axis and volume of P-3ml phase are extraordinarily compressible, showing that compression along the e axis can increase the volumetric hydrogen content for both I41/amd and P-3ml structures.
Recently, the high pressure study on the TiO_2 nanomaterials has attracted considerable attention due to the typical crystal structure and the fascinating properties of TiO_2 with nanoscale sizes. In this paper, we briefly review the recent progress in the high pressure phase transitions of TiO_2 nanomaterials. We discuss the size effects and morphology effects on the high pressure phase transitions of TiO_2 nanomaterials with different particle sizes, morphologies, and microstructures. Several typical pressure-induced structural phase transitions in TiO_2 nanomaterials are presented, including size-dependent phase transition selectivity in nanoparticles, morphology-tuned phase transition in nanowires, nanosheets,and nanoporous materials, and pressure-induced amorphization（PIA） and polyamorphism in ultrafine nanoparticles and TiO_2-B nanoribbons. Various TiO_2 nanostructural materials with high pressure structures are prepared successfully by high pressure treatment of the corresponding crystal nanomaterials, such as amorphous TiO_2 nanoribbons, α-PbO_2-type TiO_2 nanowires, nanosheets, and nanoporous materials. These studies suggest that the high pressure phase transitions of TiO_2 nanomaterials depend on the nanosize, morphology, interface energy, and microstructure. The diversity of high pressure behaviors of TiO_2 nanomaterials provides a new insight into the properties of nanomaterials, and paves a way for preparing new nanomaterials with novel high pressure structures and properties for various applications.
The high-pressure behavior of solid hydrogen has been investigated by in situ Raman spectroscopy upon compression to 300 GPa at ambient temperature. The hydrogen vibron frequency begins to decrease after it initially increases with pressure up to 38 GPa. This softening behavior suggests the weakening of the intramolecular bond and the increased intermolecular interactions. Above 237 GPa, the vibron frequency softens very rapidly with pressure at a much higher rate than that of phase HI, corresponding to transformation from phase III into phase IV. The phase transition sequence has been confirmed from phase I to phase III and then to phase IV at 208 and 237 GPa, respectively. Previous theoretical calculations lead to the proposal of an energetically favorable monoclinic C2/c structure for phase HI and orthorhombic Pbcn structure for phase IV. Up to 304 GPa, solid hydrogen is not yet an alkali metal since the sample is still transparent.
In situ high pressure XRD diffraction and Raman spectroscopy have been performed on 12 nm CeO2 nanoparticles. Surprisingly, under quasihydrostatic conditions, 12 nm CeO2 nanoparticles maintain the fluorite- type structure in the whole pressure range （0-51 GPa） during the experiments, much more stable than the bulk counterpart （PT-31 GPa）. In contrast, they experienced phase transition at pressure as low as 26 GPa under non- hydrostatic conditions （adopting CsC1 as pressure medium）. Additionally, 32-36 nm CeO2 nanoparticles exhibit an onset pressure of phase transition at 35 GPa under quasihydrostatic conditions, and this onset pressure is much lower than our result. Further analysis shows both the experimental condition （i.e., quasihydrostatic or non-hydrostatic） and grain size effect have a significant impact on the high pressure behaviors of CeO2 nanomaterials.
Fullerene molecules are interesting materials because of their unique structures and properties in mechanical, electrical, magnetic, and optical aspects. Current research is focusing on the construction of well-defined fullerene nano/microcrystals that possess desirable structures and morphologies. Further tuning the intermolecular interaction of the fullerene nano/microcrystals by use of pressure is an efficient way to modify their structures and properties, such as creation of nanoscale polymer structures and new hybrid materials, which expands the potential of such nanoscale materials for di- rect device components. In this paper, we review our recent progress in the construction of fullerene nanostructures and their structural transformation induced by high pressure. Fullerene nano/microcrystals with controllable size, morphology and structure have been synthesized through the self-assembly of fullerene molecules by a solvent-assisted method. By virtue of high pressure, the structures, components, and intermolecular interactions of the assemblied fullerene nano/microcrystals can be finely tuned, thereby modifying the optical and electronic properties of the nanostructures. Several examples on high pressure induced novel structural phase transition in typical fullerene nanocrystals with C60 or C70 cage serving as build- ing blocks are presented, including high pressure induced amorphization of the nanocrystals and their bulk moduli, high pressure and high temperature （HPHT） induced polymerization in C60 nanocrystals, pressure tuned reversible polymeriza- tion in ferrocene-doped C60/C70 single crystal, as well as unique long-range ordered crystal with amorphous nanoclusters serving as building blocks in solvated C60 crystals, which brings new physical insight into the understanding of order and disorder concept and new approaches to the design of superhard carbon materials. The nanosize and morphology effects on the transformations of fullerene nanocrystals have also been discussed. These results provide th
High pressure supramolecular chemistry is a developing interdisciplinary field. The use of high pressure for the study and fabrication of supramolecular systems has been explored only in the past few years. Such studies would shed light on the nature of the structures and functions of the complex supramolecular architectures. In this review, systematic progress made in this field is introduced based on the recent achievements. Special attention is paid to pressure-driven novel properties and functions of supramolecular assemblies resulting from the changes of molecular conformations, intermolecular interactions and supramolecular arrangements under high pressure.
Kai WangShourui LiXiao TanGuanjun XiaoBingbing LiuBo Zou
Structures of ammonium bromide under high pressure were investigated through ab initio evolutionary algorithm and total-energy calculations based on density functional theory. Static enthalpy calculations indicate that the low-pressure phase V(space group P4/nmm) transforms into a monoclinic P21/m structure at 71 GPa and then an orthorhombic structure Cmma at 130 GPa, which is found to be energetically stable up to 264 GPa. Mechanism of phonon softening at the P4/nmm P21/m transformation is discussed. Ab initio calculations show that the band overlap in the molecular Cmma phase, which causes the pressure-induced insulator-to-metal transition, occurs at about 240 GPa. Enthalpy calculations show that Cmma NH4 Br becomes unstable and dissociates into NH3 and HBr above 264 GPa.
Fu-Bo TianDa LiDe-Fang DuanChang-Bo ChenZhi HeXiao-Jing ShaZhong-Long ZhaoBing-Bing LiuTian Cui
