Theoretical study on the sound absorption of electrolytic solutions. II. Assignments of relaxations

The theory on the ultrasonic absorption spectrum of electrolytic solutions recently proposed by us is applied to the model system that resembles to the aqueous solution of MgSO4. The charges on ions are reduced to +/-1.5e in order to obtain the equilibrium structure by the integral equation theory. The theory reproduces the existence of two relaxations around 100 kHz and 1 GHz. The physical origin of the relaxation is analyzed based on the theoretical expression. The slower relaxation is shown to originate in the formation of contact ion pair, in harmony with the conventional assignment. The amplitude of this relaxation agrees with the experimental one fairly well. The absorption cross section is a weakly increasing function of the concentration of the salt in theory, whereas it depends little on the concentration in experiment, which is ascribed to the weaker association of the pair in the theory. The deviation from the Debye relaxation is found for the faster process, and the concentration dependence is small. The analysis shows that this relaxation stems from the coupling between the pressure and the long-range concentration fluctuation, and the concentration independence and the non-Debye relaxation are explained based on the theoretical analysis. In particular, the theory demonstrates that this process has the t(-3/2) tail in the time domain, which is confirmed by numerical calculation. The deviation of the theoretical relaxation amplitude from the experimental one is elucidated in terms of the theoretical expression of the coefficient.     

Reversible redox processes of poly(anilines) in layered semiconductor niobate films under alternate UV-vis light illumination

The synthesis of polyaniline (PANI) with semiconducting layered niobate (NbO) to form PANI/NbO hybrid materials and their reversible color change under a unique redox process under the influence of UV and/or visible light have been investigated. The in-situ polymerization of anilinium chlorides (ANI) packed in a regular orientation in a bilayer structure within the NbO interlayers led to PANI/NbO hybrid powders by heat treatment using (NH(4))(2)S(2)O(8) as the catalyst. The resulting PANI of these hybrids showed the characteristics of a fully oxidized quinoid form, i.e., pernigranine (PG). The PANI/NbO suspension in H(2)O was cast on a glass substrate to form a PANI/NbO film after evaporation of the water with a good parallel orientation of the NbO layers against the glass substrate. Upon UV light irradiation in the presence of a reductant such as MeOH, the violet-colored PANI (PG) polymers within the NbO interlayers were reduced by the NbO-induced photocatalytic reactions and led to a colorless PANI, i.e., leucoemeraldine (LE). Moreover, the resulting colorless PANI/NbO films reverted back to a blue-colored PANI, i.e., emeraldine (EM), due to oxidation by the surrounding O(2) gas. The PANI/NbO hybrid films were able to retain repetitive and reversible photoinduced patterning for over 50 cycles under such alternate UV and visible light irradiation.     

Effects of electric and magnetic fields on the electronic properties of zigzag carbon and boron nitride nanotubes

We have investigated the electronic properties of zigzag CNTs and BNNTs under the external transverse electric field and axial magnetic field, using tight binding approximation. It was found that after switching on the electric and magnetic fields, the band modification such as distortion of the degeneracy, change in energy dispersion, subband spacing and band gap size reduction occurs. The band gap of zigzag BNNTs decreases linearly with increasing the electric field strength but the band gap variation for CNTs increases first and later decreases (Metallic) or first hold constant and then decreases (semiconductor). For type (II) CNTs, at a weak magnetic field, by increasing the electric field strength, the band gap remains constant first and then decreases and in a stronger magnetic field the band gap reduction becomes parabolic. For type (III) CNTs, in any magnetic field, the band gap increases slowly until reaches a maximum value and then decreases linearly. Unlike to CNTs, the magnetic field has less effects on the BNNTs band gap variation.     

Synthesis of nickel(II) azacorroles by Pd-catalyzed amination of α,α'-dichlorodipyrrin Ni(II) complex and their properties

Synthesis of nickel(II) complexes of meso-aryl-substituted azacorroles was performed by Buchwald-Hartwig amination of a dipyrrin Ni(II) complex with benzylamine through C-N and C-C coupling. The highly planar structure of Ni(II) azacorroles was elucidated by X-ray diffraction analysis. (1)H?NMR analysis and nucleus independent chemical shift (NICS) calculation on Ni(II) azacorrole revealed its distinct aromaticity with [17]triaza-annulene 18π conjugation. In addition, acylation of azacorrole selectively afforded N- and C-acylated azacorroles depending on the reaction conditions, showing the dual reactivity of azacorroles.     

Mechanistic study on the reaction of pinB-BMes2 with alkynes based on experimental investigation and DFT calculations: gradual change of mechanism depending on the substituent

Transition metal-free direct and base-catalyzed 1,2-diborations of arylacetylenes using pinB-BMes₂ provided a syn/anti-isomeric mixture of diborylalkenes. The kinetic analysis showed that the reaction rate and isomer ratio were affected by reaction conditions and substituents on the aryl ring. DFT calculations indicated that direct addition proceeded via the interaction of acetylene-π with the BMes₂ fragment. In contrast, for the base-catalyzed diboration, the previously isolated sp²–sp³ diborane and borataallene were confirmed as stable intermediates by calculations. The whole reaction pathways can be divided into the Bpin-migration and deprotonation steps, where the borataallene should be considered as a common intermediate. It should be noted that the deprotonation step is reversible and affords the kinetically less favoured isomer under the thermodynamic conditions. As a result, the composition of isomeric products, in the base-catalyzed diboration, is attributed to the small difference of activation barriers between direct and base-catalyzed systems.

Combination of kinetic and DFT studies revealed a subtle balance for substituent effect toward the regioselectivity of the product in metal-free and base-catalyzed diboration of arylacetylenes.     

Observation of ferri-nonmagnetic boundary in CrPt3 line-and-space patterned media using a dark-field transmission electron microscope

Ion beam patterned CrPt₃ films were prepared by Kr⁺ ion irradiation at a dose of 2×10¹⁴ ions/cm² onto L1₂-ordered CrPt₃ whose surface was partially masked by electron beam patterned resists. Cross-sectional observation using transmission electron microscopy was carried out to study the patterning boundary of the CrPt₃ film. Dark-field imaging showed a distinct contrast between non-irradiated (L1₂ phase) and irradiated (A1 phase) regions. The transition width between the two phases was estimated to be about 5 nm, which agreed well with the value simulated by a transport ion in matter (TRIM) code simulation.     

A variant of the IDR(s) method with the quasi-minimal residual strategy

The IDR($s$) method proposed by Sonneveld and van Gijzen is an effective method for solving nonsymmetric linear systems, but usually with irregular convergence behavior. In this paper, we reformulate the relations of residuals and their auxiliary vectors generated by the IDR($s$) method in matrix form. Then, using this new formulation and motivated by other QMR-type methods, we propose a variant of the IDR($s$) method, called QMRIDR($s$), for overcoming the disadvantage of its irregular convergence behavior. Both fast and smooth convergence behaviors of the QMRIDR($s$) method can be shown. Numerical experiments are reported to show the efficiency of our proposed method.     

Solution of generalized shifted linear systems with complex symmetric matrices

We develop the shifted COCG method [R. Takayama, T. Hoshi, T. Sogabe, S.-L. Zhang, T. Fujiwara, Linear algebraic calculation of Green’s function for large-scale electronic structure theory, Phys. Rev. B 73 (165108) (2006) 1–9] and the shifted WQMR method [T. Sogabe, T. Hoshi, S.-L. Zhang, T. Fujiwara, On a weighted quasi-residual minimization strategy of the QMR method for solving complex symmetric shifted linear systems, Electron. Trans. Numer. Anal. 31 (2008) 126–140] for solving generalized shifted linear systems with complex symmetric matrices that arise from the electronic structure theory. The complex symmetric Lanczos process with a suitable bilinear form plays an important role in the development of the methods. The numerical examples indicate that the methods are highly attractive when the inner linear systems can efficiently be solved.     

Effect of diffusion-induced bending on diffusion-induced stress near the end faces of an elastic hollow cylinder

Diffusion-induced stress plays an important role in determining structural integrity of mechanical structures used in lithium-ion batteries and microelectromechanical devices. Incorporating the diffusion-induced bending in the analysis of the diffusion-induced stress in an elastic hollow cylinder, analytical forms of the diffusion-induced resultant axial stress and hoop stress have been formulated for the traction-free condition and the built-in condition at the end faces of the cylinder. Using these results, the evolution of the diffusion-induced stress at the end faces of a hollow, elastic electrode due to the insertion of lithium is discussed under the potentiostatic operation. The end faces of the electrode experience compressive hoop stress through the thickness in contrast to the stress state in the hollow cylinder far away from the end faces. The magnitude of the resultant hoop stress decreases with increasing the diffusion time for the traction-free end faces; it increases with increasing the diffusion time near the inner surface for the built-in end faces.     

Simultaneous measurement of velocity and pressure in a plane jet

A new technique was developed for the simultaneous measurement of velocity and pressure in turbulent flows. To accomplish this objective, a new probe (hereafter called the combined probe) that consists of an X-type hot-wire probe and a newly devised pressure probe was developed. The pressure probe was miniaturized by the MEMS fabrication process and by using a 0.1-in. microphone as a pressure sensor for improving the spatial resolution. This pressure probe was placed between two hot-wire sensors of which the X-type hot-wire probe was composed. The pressure probe was given a hemispherical tip, like that of a pitot tube, because an earlier pressure probe with a conical tip suffered from a reduction in spatial resolution. The spatial arrangement of the pressure probe and the hot-wire probe for the combined probe was carefully determined, because there was a risk that the measurement accuracy of one probe will be influenced by disturbances caused by the other probe when the two probes were placed very close to each other. Therefore, the combined probe was arranged to engender no noticeable interference between the velocity data and the pressure data measured by their respective probes. As one application of this combined probe, simultaneous measurements of pressure and two components of instantaneous velocity were performed in a plane jet. The turbulent energy budget and the cross-correlation coefficient of velocity and pressure in the intermittent region of the plane jet were estimated. The results show that the mean streamwise velocity, velocity fluctuation, and pressure fluctuation profiles were consistent with those measured individually using the X-type hot-wire probe or pressure probe. Moreover, it was shown that the integral value of the diffusion term (which should theoretically be equal to zero) in the turbulent energy transport equation was closer to zero than previous reports (Bradbury in J Fluid Mech 23(Part 1):31–64, 1965). In addition, the time variation of the cross-correlation coefficient in the intermittent region supports the vortex structure model predicted in previous studies (Browne et?al. in J Fluid Mech 149:355–373, 1984; Tanaka et?al. JSME Int J Ser B 49(4):899–905, 2006; Sakai et?al. J Fluid Sci Technol 2(3):611–622, 2007).