Formation and reactions of aryldiazomethane radical cations

Dicyanoanthracene-sensitized photolysis of aryldiazomethanes affords stilbenes with cis/trans ratios of ～3 via free radical cations; anodic oxidation gives similar results but via radical cations adsorbed on electrode surface.     

Multiphoton transitions in a macroscopic quantum two-state system

We have observed multiphoton transitions between two macroscopic quantum-mechanical superposition states formed by two opposite circulating currents in a superconducting loop with three Josephson junctions. Resonant peaks and dips of up to three-photon transitions were observed in spectroscopic measurements when the system was irradiated with a strong rf-photon field. The widths of the multiphoton absorption dips are shown to scale with the Bessel functions in agreement with theoretical predictions derived from the Bloch equation or from a spin-boson model.     

Search for electron neutrino appearance in a 250 km long-baseline experiment

We present a search for electron neutrino appearance from accelerator-produced muon neutrinos in the K2K long-baseline neutrino experiment. One candidate event is found in the data corresponding to an exposure of 4.8 x 10(19) protons on target. The expected background in the absence of neutrino oscillations is estimated to be 2.4+/-0.6 events and is dominated by misidentification of events from neutral current pi(0) production. We exclude the nu(micro) to nu(e) oscillations at 90% C.L. for the effective mixing angle in the 2-flavor approximation of sin((2)2theta(microe)( approximately 1/2sin((2)2theta(13))>0.15 at Deltam(2)(microe)=2.8 x 10(-3) eV(2), the best-fit value of the nu(micro) disappearance analysis in K2K. The most stringent limit of sin((2)2theta(microe)<0.09 is obtained at Deltam(2)(microe)=6 x 10(-3) eV(2).     

Single-crystal growth, crystal and electronic structure of NaCoO2

Single crystals of NaCoO₂ have been successfully synthesized for the first time by a flux method at 1323 K. A single-crystal X-ray diffraction study confirmed the trigonal space group and the lattice parameters , . The crystal structure has been refined to the conventional values R=1.9% and wR=2.1% for 309 independent observed reflections. The electron density distribution of NaCoO₂ has been studied by the maximum entropy method (MEM) using single-crystal X-ray diffraction data obtained at 298 K. From the results of the MEM analysis, the strong covalent bonding was clearly observed between Co and O atoms, while no bonding was observed around Na atoms. We also calculated the electron density of NaCoO₂ by first principles calculations. The electron density obtained experimentally is in good agreement with the theoretical one.     

Comparative Study of Influence of Simultaneous Modulation of Upper-Coil and Lower-Coil Currents on Silicon Nanoparticles Synthesized Using Tandem-Type Modulated Induction Thermal Plasmas

Plasma Chemistry and Plasma Processing - The influences of upper-coil and lower-coil current modulation of tandem-type modulated induction thermal plasma (tandem-MITP) were studied for silicon...     

Measurement of tonal-noise characteristics and periodic flow structure around NACA0018 airfoil

The characteristics of tonal noise and the variations of flow structure around NACA0018 airfoil in a uniform flow are studied by means of simultaneous measurement of noise and velocity field by particle-image velocimetry to understand the generation mechanism of tonal noise. Measurements are made on the noise characteristics, the phase-averaged velocity field with respect to the noise signal, and the cross-correlation contour of velocity fluctuations and noise signal. These experimental results indicate that the tonal noise is generated from the periodic vortex structure on the pressure surface of the airfoil near the trailing edge of the airfoil. It is found that the vortex structure is highly correlated with the noise signal, which indicates the presence of noise-source distribution on the pressure surface. The vorticity distribution on the pressure surface breaks down near the trailing edge of the airfoil and forms a staggered vortex street in the wake of the airfoil.     

Three‐dimensional reference interaction site model self‐consistent field analysis of solvent and substituent effects on the absorption spectra of Brooker's merocyanine

Solvent and substituent effects on the absorption spectra of Brooker's merocyanine (BM) are investigated using the three‐dimensional reference interaction site model self‐consistent field method and time‐dependent density functional theory. The π–π* excitation energies are computed for BM and its derivative 2,6‐di‐tert‐butyl (di‐t‐Bu) BM. The behaviors of the computed excitation energies with increasing solvent polarity are in good agreement with those of the corresponding experimental measurements. In addition, analysis of the solute–solvent interaction energies and spatial distribution functions reveals that the effects of the solvent on the absorption spectra are reduced by the steric hindrance of the t‐Bu groups. Furthermore, from the difference in the solute–solvent interaction energies of BM and di‐t‐Bu BM, it is shown that the effect of the t‐Bu substituents on the absorption spectrum is greater in high‐polarity solvents. © 2015 Wiley Periodicals, Inc.     

Development of spin‐dependent relativistic open‐shell Hartree–Fock theory with time‐reversal symmetry (I): The unrestricted approach

An open‐shell Hartree–Fock (HF) theory for spin‐dependent, two‐component relativistic calculations, termed the Kramers‐unrestricted HF (KUHF) method, is developed. The present KUHF method, which is formulated as a relativistic counterpart of nonrelativistic UHF, is based on quaternion algebra and partly uses time‐reversal symmetry. The fundamental characteristics of KUHF are discussed in this study. From numerical assessments, it was revealed that KUHF gives a corresponding solution to nonrelativistic UHF; furthermore, KUHF properly describes spin‐orbit interactions. In addition, KUHF can improve the self‐consistent field convergence behavior in spin‐dependent calculations, for example, for f‐block elements.     

Tetracyclopenta[def,jkl,pqr,vwx]tetraphenylene: A Potential Tetraradicaloid Hydrocarbon

A tetramesityl derivative of hitherto unknown tetracyclopenta[def,jkl,pqr,vwx]tetraphenylene (TCPTP), which is a potential tetraradicaloid hydrocarbon, was synthesized. Theoretical calculations based on spin‐flip time‐dependent density functional theory predict that the closed‐shell D_2h form of TCPTP is more stable than the open‐shell D_4h form with its slightly tetraradical character. The tetramesityl derivative (Mes)₄‐TCPTP exhibits remarkable antiaromaticity as a result of the peripheral 20‐π‐electron circuit, which causes an absorption maximum at a long wavelength and a small HOMO–LUMO gap. In solution, (Mes)₄‐TCPTP most likely adopts rapidly equilibrating D_2h structures that interconvert via the D_4h transition state. X‐ray crystallographic analysis showed (Mes)₄‐TCPTP as an approximate D_2h structure.