Transition metal-metal oxide hybrids as versatile materials for hydrogen storage

Metal atom located on metal oxide (MMO) is a promising material with various applications such as hydrogen storage. As one of the metal oxides, niobium oxide (NbO) presents fascinating properties that make it a possibly applicable in MMOs. Here, we investigated the feasibility of transition metal-NbO hybrids as MMO materials for application in the hydrogen storage technology. In this respect, the hydrogen adsorption of transition metals (Fe, Ni, Cu, Pd, Ag, and Pt) decorated on the NbO nanocluster has been explored using density functional theory calculations. We found that the adsorption energy of the H₂ molecule on the NbO adsorbent is remarkably increased by locating the transition metals on the NbO metal oxide. Our results reveal that the transition metals decorated on the NbO nanocluster can act as active sites for hydrogen adsorption. Among the studied transition metals, Pt shows the highest hydrogen capacity up to 6.52 wt%.     

Electronic structure of Ru impurities in iron

The molecular cluster discrete variational method has been employed to study the magnetic properties of Ru impurities and Ru monolayers in iron. With the introduction of Ru atoms in the neighborhood of an Fe atom the local moment changes appreciably and the magnetization decreases steadily. By increasing Ru concentration both ferromagnetic and antiferromagnetic Fe–Ru couplings can be expected in dilute alloys. The calculations indicate that the contact hyperfine fields of Fe atoms are strongly dependent on the chemical environment as well as on the local symmetry.     

Zirconium-assisted reaction in low temperature atomic layer deposition using Bis(ethyl-methyl-amino)silane and water

The reaction of Bis(ethyl-methyl-amino)silane (BEMAS) and water in atomic layer deposition (ALD) became possible when Zr-containing species were adsorbed on the vacant sites of the surface after a pulse and purge of BEMAS. The growth rates of the Si(Zr)O_x films were 0.8-0.9 nm/cycle in the temperature range of 185-325 °C. This phenomenon probably originates from the highly reactive hydroxyl species generated by Zr atoms. From this point of view, transition metals make reactant gas molecules to be highly activated in the ALD processes of transition metal oxides and nitrides, which might be an important factor that determines the ALD characteristics.     

Metal-Free,Visible-Light-Induced Selective C−C Bond Cleavage of Cycloalkanones with Molecular Oxygen

A metal-free, visible-light-induced oxidative C−C bond cleavage of cycloketones with molecular oxygen is described. Cooperative Brønsted-acid catalysis and photocatalysis enabled selective C−C bond cleavage of cycloketones to generate an array of γ-, δ- and ϵ-keto esters under very mild conditions. Mechanistic studies indicate that singlet molecular oxygen (¹O₂) is responsible for this transformation.     

High Pressure Theoretical Studies of Actinide Dioxides

Actinide dioxides (ThO 2 , UO 2 , Pu 2 etc.) compounds have the CaF 2 -type structure at ambient pressure and temperature. Under high pressure, they exist in the PbCl 2 -type structure, belonging to space group Pnma [1]. We have studied crystal structures under high pressure in actinide dioxides by means of first-principles self-consistent total-energy calculations with the non-local Perdew, Burke and Ernzerhof (PBE) exchange correlation using the full-potential linear-muffin-tin-orbital (FPLMTO) method. The atomic equilibrium volume, bulk modulus and transition pressure for actinide dioxides were calculated, covering the full pressure range for which the mentioned experiments have been done [2].     

Hierarchic Natures and Dynamics of Photoinduced Structural Phase Transition in Non-Degenerate Charge Density Wave States Via Successive Photoexcitations

We investigate the adiabatic and dynamical natures of the lattice relaxation of excitons in strongly coupled electron-phonon (e-ph) systems using the extended Peierls-Hubbard model, so as to clarify the possible mechanisms of the photoinduced structural phase transition (PISPT) via multi-photon. Focusing on the growth process of relaxed domains that is induced by multi-photoexcitation, we calculate the adiabatic potential energy surfaces relevant to the nonlinear lattice relaxations of excitons in this process. Calculated potentials lead to an essential model of a multi-stepwise potential-crossing (MSPC) system that is composed of many displaced harmonic oscillators as an elementary process of the domain growth in the strongly coupled e-ph systems. We also investigate the dynamical natures in such MSPC systems calculating the time-developments the excited wave packet in this system using the density operator. It is concluded from calculated results that the system possibly develops from the lowest-energy potential state to the higher ones by the effect of the photoexcitations followed by the lattice relaxations.     

Density studies across the smectic G-nematic and nematic-lsotropic transitions

The densities of N(p-n-pentyloxy benzylidene) p-ethylaniline and N(p-n-hexyloxy benzylidene) p-ethylaniline are measured as a function of temperature from the isotropic liquid to the smectic G phase. Both the compounds exhibit enantiotropic smectic G and nematic liquid crystalline phases. The changes in density across the phase transformations and the thermal expansion coefficient confirm the order of the transitions as of first order. The particular importance of the smectic G to nematic transformation is apparent from the density jump across the transition. An estimate of the pressure dependence of the isotropic-nematic transition temperature is found to be in reasonable accord with the literature data.     

关于非负下半连续函数最优可测耦合的存在性及其应用

本文证明了两个转移概率关于非负下半连续函数最优可测耦合的存在性定理．作为对这一结果的应用,推广了Ｓｔｒａｓｓｅｎ定理,进而证明了跳过程的随机可比性等价于保序耦合的存在性．     

Magnetocaloric effect and transition order of Mn5Ge3 ribbons

Single phase Mn₅Ge₃ ribbons were successfully synthesized by single roller melt-spinning method followed by an annealing procedure at 800 °C for 1 h. The magnetocaloric effect and transition order were investigated by dc magnetization measurement. A maximum entropy change of 4.92 J/kg K and a refrigerant capacity of 201.3 J/kg were observed at an external field change of 30 kOe. The Banerjee criterion was adopted to discriminate the order of the transition, indicating a second order transition. The calculated entropy changes were also obtained by Landau theory, which are in agreement with the experimental values at the temperature region above the Curie temperature. This phenomena implies a potential transition of the magnetic interaction in the vicinity of the Curie temperature. Universal behavior was also indicated in that all of the experimental entropy change curves collapse into one universal curve, which is consistent with the Banerjee criterion.     

Magnetic molecular wheels and grids - the need for novel concepts in “zero-dimensional” magnetism

Supramolecular chemistry has allowed the production, by self-assembly, of inorganic complexes with a [N × N] square matrix-like configuration of N² metal centers. Interest in these systems is driven by the potential applications in information technology suggested by such a “two-dimensional” (2D), addressable arrangement of metal ions. From the magnetic perspective [N × N] grids constitute molecular model systems for magnets with extended interactions on a square lattice, which have gained enormous attention in the context of high-temperature superconductors. Numerous [2 × 2] grids as well as a few [3 × 3] grids with magnetic metal ions such as Cu(II), Ni(II), Co(II), Fe(II), and Mn(II) have been created. Magnetic studies unraveled a remarkable variety in their magnetic properties, which will be reviewed in this work with emphasis on the underlying physical concepts. An intriguing issue is the connection of [2 × 2] and [3 × 3] grids with “one-dimensional” (1D) rings, as experimentally realized in the molecular wheels. For a [2 × 2] square of spin centers the distinction between a 2D grid and a 1D ring is semantic, but also a [3 × 3] grid retains 1D character: it is best viewed as an octanuclear ring with an additional ion “doped” into its center. Challenging familiar concepts from conventional magnets, the current picture of elementary excitations in antiferromagnetic rings will be discussed, as a prerequisite to understand the complex [3 × 3] grids.