Structure refinement of sub-cubic-mm volume sample at high pressures by pulsed neutron powder diffraction: application to brucite in an opposed anvil cell

Neutron powder diffraction measurements of 0.9 mm³ of mixture of deuterated brucite and pressure medium were conducted at pressures to 2.8 GPa, using an opposed anvil cell and a medium-resolution diffractometer at Japan Proton Accelerator Research Complex pulsed neutron source. Spurious-free diffraction patterns were successfully obtained and refined to provide all structural parameters including Debye–Waller factors. Tilting of hydroxyl dipoles of brucite toward one of the three nearest-neighbor oxygen anions was confirmed to be substantial at pressure as low as 1.5 GPa. By this application, technical feasibility to analyze such a small sample has been newly established, which would be useful to extend the applications of neutron diffraction at high pressures.     

Boltzmann equation in de Sitter space

In a time dependent background like de Sitter space, Feynman–Dyson perturbation theory breaks down due to infra-red divergences. We investigate an interacting scalar field theory in Schwinger–Keldysh formalism. We derive a Boltzmann equation from a Schwinger–Dyson equation inside the cosmological horizon. Our solution shows that the particle production is compensated by the reduction of the on-shell states due to unitarity. Although the degrees of freedom inside the horizon leads to a small and diminishing screening effect of the cosmological constant, there is a growing screening effect from those outside the horizon.     

Index Abstracts

Abstract

Calorimetric titrations have been performed in anhydrous acetonitrile at 25°C to give the complex stability constants (K _s) and the thermodynamic parameters (ΔGΔ, ΔHΔ and ΔSΔ) for the complexation of light lanthanoid(III) nitrates (La-Gd) with N-benzylaza-21-crown-7 3. Data analyses, assuming 1:1 stoichiometry, were successfully applied to all light lanthanoid-azacrown ether combinations employed. Using the present and previous data on 15- to 21- membered N-benzylazacrown ethers 1–3, the effect of ring size upon complexation behavior was discussed comparatively and globally from the thermodynamic point of view. The complexation behaviors are analyzed in terms of the size-fit concept, N-substituent coordination numbers, and lanthanoid's surface charge density. Thermodynamically the complexation of light lanthanoids with azacrown ethers is enthalpy-driven, while the cation selectivity is generally entropy-driven in acetonitrile.     

A Doping Technique that Suppresses Undesirable H2 Evolution Derived from Overall Water Splitting in the Highly Selective Photocatalytic Conversion of CO2 in and by Water

Photocatalytic conversion of CO₂ to reduction products, such as CO, HCOOH, HCHO, CH₃OH, and CH₄, is one of the most attractive propositions for producing green energy by artificial photosynthesis. Herein, we found that Ga₂O₃ photocatalysts exhibit high conversion of CO₂. Doping of Zn species into Ga₂O₃ suppresses the H₂ evolution derived from overall water splitting and, consequently, Zn‐doped, Ag‐modified Ga₂O₃ exhibits higher selectivity toward CO evolution than bare, Ag‐modified Ga₂O₃. We observed stoichiometric amounts of evolved O₂ together with CO. Mass spectrometry clarified that the carbon source of the evolved CO is not the residual carbon species on the photocatalyst surface, but the CO₂ introduced in the gas phase. Doping of the photocatalyst with Zn is expected to ease the adsorption of CO₂ on the catalyst surface.     

Colossal magnetoresistance without phase separation: disorder-induced spin glass state and nanometer scale orbital-charge correlation in half doped manganites

The magnetic and electrical properties of high-quality single crystals of A-site disordered (solid solution) Ln0.5Ba0.5MnO3 are investigated near the phase boundary between the spin-glass insulator and colossal-magnetoresistive ferromagnetic metal, locating near Ln=Sm. The temperature dependence of the ac susceptibility and the x-ray diffuse scattering of Eu0.5Ba0.5MnO3 are analyzed in detail. The uniformity of the random potential perturbation in Ln0.5Ba0.5MnO3 crystals with a small bandwidth yields, rather than the phase separation, an homogeneous short ranged charge or orbital order which gives rise to a nearly atomic spin-glass state. Remarkably, this microscopically disordered "charge-exchange-glass" state alone is able to bring forth the colossal magnetoresistance.     

A compact permanent‐magnet system for measuring magnetic circular dichroism in resonant inelastic soft X‐ray scattering

A compact and portable magnet system for measuring magnetic dichroism in resonant inelastic soft X‐ray scattering (SX‐RIXS) has been developed at the beamline BL07LSU in SPring‐8. A magnetic circuit composed of Nd–Fe–B permanent magnets, which realised ～0.25 T at the center of an 11 mm gap, was rotatable around the axis perpendicular to the X‐ray scattering plane. Using the system, a SX‐RIXS spectrum was obtained under the application of the magnetic field at an angle parallel, nearly 45° or perpendicular to the incident X‐rays. A dedicated sample stage was also designed to be as compact as possible, making it possible to perform SX‐RIXS measurements at arbitrary incident angles by rotating the sample stage in the gap between the magnetic poles. This system enables facile studies of magnetic dichroism in SX‐RIXS for various experimental geometries of the sample and the magnetic field. A brief demonstration of the application is presented.     

Numerical study on trapping and guiding of nanoparticles in a flow using scattering field of laser light

Optical trapping and guiding using laser have been proven to be useful for non-contact and non-invasive manipulation of small objects such as biological cells, organelles within cells, and dielectric particles. We have numerically investigated so far the motion of a Brownian particle suspended in still water under the illumination of a speckle pattern generated by the interference of coherent light scattered by a rough object. In the present study, we investigate numerically the motion of a particle in a water flow under the illumination of a speckle pattern that is at rest or in motion. Trajectory of the particle is simulated in relation with its size, flow velocity, maximum irradiance, and moving velocity of the speckle pattern to confirm the feasibility of the present method for performing optical trapping and guiding of the particle in the flow.     

Extended Fluorochromism of Anthracene Trimers with a meta‐Substituted Triphenylamine or Triphenylphosphine Core

Combining meta‐triphenylamine or triphenylphosphine with three anthracene fluorophores gives rise to fluorescent non‐planar triskelions 1 and 2 . The emissive properties of 1 are highly solvatochromic, yielding blue to pale green and even pale yellow fluorescence, whereas the blue emission of 2 is solvent‐insensitive. Anthracene trimers 1 and 2 are both emissive in the solid state, displaying yellow and pale green fluorescence, respectively, with moderate quantum yields.     

Alkylation‐, Heating‐, and Doping‐Induced Emission Enhancement of a Polyaromatic Tube in the Solid State

A polyaromatic tube with a subnanometer‐sized cavity was efficiently prepared on a gram‐scale through the stereo‐controlled cyclotrimerization of a diphenylanthracene derivative as a key step. The facile exterior alkylation of the polyaromatic framework leads to a moderately fluorescent tube (R=‐OC₁₀H₂₁; Φ_F=20 %) in the solid state. The emission intensity of the solid‐state alkyl‐substituted tube is remarkably enhanced upon heating (up to 1.6 times, Φ_F=31 %) as well as doping with fluorescent dyes (up to 4.2 times, Φ_F=83 %) through efficient energy transfer.