Determination of the rate constants of the reactions of NO3 radical with CF3I and I(2P3/2)

The rate constant of the reaction of NO₃ radical with CF₃I was determined by a relative rate method using a Fourier transform infrared (FTIR) spectrometer smog chamber with a long path length gas cell. As a result, the upper limit of the rate constant was determined to be <2.2 × 10^?18 cm³ molecule^?1 s^?1 in 100 Torr of total pressure at 298 K, which suggests that CF₃I emitted into the atmosphere accumulates during night. The rate constant of the reaction of NO₃ with I(²P_3/2) was also measured using time‐resolved cavity ring‐down spectroscopy. The rate constant showed no pressure dependence in the range of 100–500 Torr of total pressure at 298 K and was determined to be (3.9 ± 1.0) × 10^?11 cm³ molecule^?1 s^?1. The present result is different from the previous ones and is about half of that reported most recently. From this rate constant, it is likely that the reaction of NO₃ radical with I(²P_3/2) does not have a much influence on the loss of I(²P_3/2) and the formation cycle of IO radical in the atmosphere. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 649–660, 2012     

X-ray absorption spectral analyses by theoretical calculations for TiO2 and Ni-doped TiO2 thin films on glass plates.

Ni L- and Ti L-edge as well as Ti K-edge X-ray absorption experiments for TiO2 thin films and Ni-doped TiO2 thin films coated on glass plates were performed using synchrotron radiation to investigate the structures around Ni and Ti ions in the films. The obtained spectra were compared with the results of theoretical calculations. It has consequently been found that the spectral features were affected by a change in the oxidizing form of Ni ions due to hydrogen reduction, by the charge variation and/or slight orbital splitting of Ti ions, and by the magnitude of the interaction between the center Ti ion and neighboring Ti ions.     

Catalytic Mannich-type reaction of phosphorylimidates

Phosphorylimidates reacted with N-Boc imines in the presence of a catalytic amount of potassium hexamethyldisilazide, to afford the corresponding Mannich-type adducts in high yields. It was shown that, like sulfonylimidates, phosphorylimidates can function as ester equivalents. In contrast to sulfonylimidates however, phosphorylimidates exhibited high anti-selectivity even in low polar solvents. An explanation for the anti-selectivity is given.     

Theoretical study on quantum dynamics of bose system interacting with photon field

We investigate the quantum dynamics of two‐boson and two‐level systems interacting with a one‐mode photon field. The time evolution of the population for each state is calculated in terms of the Jaynes–Cummings model. We find the collapses and revivals of the order parameter for the Bose–Einstein condensation. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 401–408, 2001     

Short communication: An alternative and effective catalyst for the silastannation of arylacetylenes with Me3SiSnBu3 at room temperature

The palladium‐catalyzed silastannation of acetylenes with tributyl(trimethylsilyl)stannane in the presence of triethylphosphite is reported for the first time. The reaction occurs at room temperature to give (Z)‐silyl(stannyl)ethenes in high yields. The protodemetallation of the resulting adducts with HCl–tetraethylammonium chloride is described first, which demonstrates that the reaction is governed only by the stability of a carbonium ion arising from the protonation to (Z)‐silyl(stannyl)ethenes rather than the hard and soft acid and base principle, i.e. the β‐cation stabilization effect (σ–π stabilization one) of a stannyl group in the carbonium ion is rather significant. Copyright © 2004 John Wiley & Sons, Ltd.     

High energy spectroscopy in Ce and La compounds

X-ray photoemission, X-ray photoabsorption and bremmstrahlung isochromat spectroscopy in Ce and La compounds are theoretically analyzed by using the single-site Anderson model incorporated with various final state interactions. Discussions are given on the physical information derived from the analysis and also on similarities and differences in spectral features between metallic and insulating systems.     

Exciton dynamics in nanostar dendritic systems using a quantum master equation approach: core monomer effects and possibility of energy transport control

The directional energy transport, i.e. exciton migration, in nanostar dendritic systems composed of two-state monomer units is studied using a quantum master equation approach. We examine the effects of the variation in the excitation energy of the monomer in the core region (core monomer) on the multistep exciton migration from the periphery to the core based on the relaxation factors among exciton states originating in weak exciton-phonon coupling. It turns out that when the core monomer possesses both an excitation energy slightly lower than that of the first generation and a partial exciton overlap with the first generation, more efficient and rapid exciton migration to the core is expected as compared with other core monomer cases with the energy level closer to or much lower than that of the first generation.     

Determination of interbilayer and transbilayer lipid transfers by time-resolved small-angle neutron scattering

We applied a time-resolved small-angle neutron scattering technique to the vesicle system of dimyristoylphosphatidylcholine for the first time to determine lipid kinetics. The observed kinetics could be explicitly represented by a simple model that includes two independent kinetic parameters, i.e., the rates of transbilayer and interbilayer exchange. This technique is perfectly suited for the determination of lipid exchange kinetics in equilibrium and applicable to evaluation of the activity of the factors relevant to lipid migration, such as translocase and lipid transfer proteins.