Biradical character of linear π-conjugated oligomer dications composed of thiophene, pyrrole, and methylthio end-capping units

Combined DFT calculations and UV-vis-NIR, ESR, and SQUID measurements revealed that the ground-state electronic structure of a linear π-conjugated oligomer dication composed of two pyrrole and six or seven thiophene rings and methylthio end-capping units is dominated by a singlet biradical character.     

Test compounds for detecting the silanol effect on the elution of ionized amines in reversed‐phase LC

The effectiveness of several basic compounds for testing silica‐based stationary phases was reviewed by applying them to recent columns for reversed‐phase HPLC. Most octadecylsilylated (C18) stationary phases, prepared as a base‐deactivated material from high‐purity silica gel with endcapping, provided excellent peak shape and column efficiency for the bases including benzylamine and amitriptyline that once caused problems and were subsequently employed for testing silanol activities. However, a cyclic tertiary amine, dextrometorphan, was eluted as an acceptable peak from only a few columns at neutral pH. Such a more sensitive probe is expected to contribute to further improvement of the stationary phase for reversed‐phase HPLC.     

Role of Ti 3d carriers in mediating the ferromagnetism of Co∶TiO2 anatase thin films

We study the surface and bulk electronic structure of the room-temperature ferromagnet Co∶TiO(2) anatase films using soft- and hard-x-ray photoemission spectroscopy with probe sensitivities of ～1 and ～10 nm, respectively. We obtain direct evidence of metallic Ti(3+) states in the bulk, which get suppressed to give a surface semiconductor, thus indicating the difference in electronic structure between surface and bulk. X-ray absorption and resonant photoemission spectroscopy reveal Ti(3+) electrons at the Fermi level (E(F)) and high-spin Co(2+) electrons occurring away from E(F). The results show the importance of the charge neutrality condition: Co(2+)+V(O)(2-)+2Ti(4+)?Co(2+)+2Ti(3+) (V(O) is oxygen vacancy), which gives rise to the elusive Ti 3d carriers mediating ferromagnetism via the Co 3d-O 2p-Ti 3d exchange interaction pathway of the occupied orbitals.     

Practical techniques for a three‐dimensional FEM analysis of incompressible fluid flow contained with slip walls and a downstream tube bundle

Two practical techniques are proposed in this paper to simulate a flow contained in a plenum with a downstream tube bundle under a PC environment. First, a technique to impose slip wall conditions on smooth‐faced planes and sharp edges is proposed to compensate for the mesh coarseness relative to boundary layer thickness. In particular, a new type of Poisson equation is formulated to simultaneously satisfy both such velocity boundary conditions on walls and the incompressibility constraint. Second, a numerical model for a downstream tube bundle is proposed, where hydraulic resistance in a tube is imposed as a traction boundary condition on a fluid surface contacting the tube bundle end. The effectiveness of the techniques is numerically demonstrated in the application to a flow in a condenser water box. Copyright © 2001 John Wiley & Sons, Ltd.     

Thin films of peroxopolytungstic acids: applications to optical waveguide components

Thin films of peroxohetero(carbon)polytungstic acid (CW-HPA) and carbon-free isopolytungstic acid (W-IPA) were prepared, and examined in terms of optical and etching properties. Thermal decomposition was found to give good results in removing excess hydrogen peroxide (H₂O₂) during the preparation of CW-HPA and W-IPA. It was shown for the first time that thin films of CW-HPA and W-IPA have very high refractive indices (larger than 2.0) when sufficiently dried. Optical waveguide (OWG) characteristics of these films were examined using a slab-type OWG structure and ARROW (Antiresonance Reflection Optical Waveguide)-type structures. An embossing technique was applied to make diffractional grating couplers.     

A new positive‐definite regularization of incompressible Navier–Stokes equations discretized with Q1/P0 finite element

A new regularization method is proposed for the Galerkin approximation of the incompressible Navier–Stokes equations with Q1/P0 element, by newly introducing a square‐type linear form into the variational divergence‐free constraint regularized with the global pressure jump (GPJ) method. The addition of the square‐type linear form is intended to eliminate the hydrostatic pressure mode appearing in confined flows, and to make the discretized matrix positive definite and then non‐singular without the pressure pegging trick. Effects of the free parameters for the regularization on the solutions are numerically examined with a 2‐D driven cavity flow problem. Furthermore, the convergences in the conjugate gradient iteration for the solution of the pressure Poisson equation are compared among the mixed method, the GPJ method and the present method for both leaky and non‐leaky 3‐D driven cavity flows. Finally, the non‐leaky 3‐D cavity flows at different Re numbers are solved to compare with the literature data and to demonstrate the accuracy of the proposed method. Copyright © 2003 John Wiley & Sons, Ltd.     

On streamline diffusion arising in Galerkin FEM with predictor/multi‐corrector time integration

In the present paper, the author shows that the predictor/multi‐corrector (PMC) time integration for the advection–diffusion equations induces numerical diffusivity acting only in the streamline direction, even though the equations are spatially discretized by the conventional Galerkin finite element method (GFEM). The transient 2‐D and 3‐D advection problems are solved with the PMC scheme using both the GFEM and the streamline upwind/Petrov Galerkin (SUPG) as the spatial discretization methods for comparison. The solutions of the SUPG‐PMC turned out to be overly diffusive due to the additional PMC streamline diffusion, while the solutions of the GFEM‐PMC were comparatively accurate without significant damping and phase error. A similar tendency was seen also in the quasi‐steady solutions to the incompressible viscous flow problems: 2‐D driven cavity flow and natural convection in a square cavity. Copyright © 2002 John Wiley & Sons, Ltd.     

The exchange interaction in the radical pair in 2-propanol solution as studied by the CIDNP multiplet pattern

The exchange interaction in the radical pair in homogeneous solution has been investigated by using the CIDNP method. The experimental observations of the multiplet pattern were compared with the theoretical simulations in which the exchange integral was a variable parameter. The results show that 2-propanol is a unique solvent in that the exchange integral in the radical pair in this solvent is large.