Rate constants for the gas‐phase reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals at 250–430 K

The rate constants k₁ for the reaction of CF₃CF₂CF₂CF₂CF₂CHF₂ with OH radicals were determined by using both absolute and relative rate methods. The absolute rate constants were measured at 250–430 K using the flash photolysis–laser‐induced fluorescence (FP‐LIF) technique and the laser photolysis–laser‐induced fluorescence (LP‐LIF) technique to monitor the OH radical concentration. The relative rate constants were measured at 253–328 K in an 11.5‐dm³ reaction chamber with either CHF₂Cl or CH₂FCF₃ as a reference compound. OH radicals were produced by UV photolysis of an O₃–H₂O–He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during the UV irradiation. The k₁ (298 K) values determined by the absolute method were (1.69 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (FP‐LIF method) and (1.72 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (LP‐LIF method), whereas the K₁ (298 K) values determined by the relative method were (1.87 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CHF₂Cl reference) and (2.12 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CH₂FCF₃ reference). These data are in agreement with each other within the estimated experimental uncertainties. The Arrhenius rate constant determined from the kinetic data was K₁ = (4.71 ± 0.94) × 10^?13 exp[?(1630 ± 80)/T] cm³ molecule^?1 s^?1. Using kinetic data for the reaction of tropospheric CH₃CCl₃ with OH radicals [k₁ (272 K) = 6.0 × 10^?15 cm³ molecule^?1 s^?1, tropospheric lifetime of CH₃CCl₃ = 6.0 years], we estimated the tropospheric lifetime of CF₃CF₂CF₂CF₂CF₂CHF₂ through reaction with OH radicals to be 31 years. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 26–33, 2004     

Polymerization of vinyl monomers by diphenylsulfone–potassium complexes

Diphenylsulfone (DPSO₂) was found to react with an equimolar amount of potassium in tetrahydrofuran (THF), dimethoxyethane (DME), or diglyme (DG) at reflux or an elevated temperature to yield a reddish-black solution, giving an electron spin resonance (ESR) signal. The signal was attributed to the formation of relatively labile DPSO₂ anion radical. The apparent effects of solvents on the reactivity of DPSO₂ with potassium depended on the polarities and the solvation powers: benzene ? toluene ? dioxane ? tetrahydrofuran < monoglyme < diglyme. The monopotassium complex was found to react further with another molecular amount of the metal to yield a dark blue solution giving no ESR signal. The monopotassium complex initiated the polymerization of acrylonitrile (AN). It did not, however, initiate the polymerization of methyl methacrylate (MMA), styrene (St), or isoprene (IP). The active species of the monopotassium complex that initiated the polymerization of AN was found from analyses of the reaction products and the infrared spectrum of oily oligomer of AN obtained by the complex to be potassium benzenesulfinate. The dipotassium complex was found to initiate the polymerization of MMA, St, IP and AN. The active species of the dipotassium complex that initiated the polymerization of MMA, St, or IP was found from analyses of the reaction products and the infrared spectrum of the oily oligomer of MMA obtained by the complex to be phenyl potassium.     

Rashba spin-orbit coupling probed by the weak antilocalization analysis in InAlAs/InGaAs/InAlAs quantum wells as a function of quantum well asymmetry

We have investigated the values of the Rashba spin-orbit coupling constant alpha in In(0.52)Al(0.48)As/In(0.53)Ga(0.47)As/In(0.52)Al(0.48)As quantum wells using the weak antilocalization (WAL) analysis as a function of the structural inversion asymmetry (SIA) of the quantum wells. We have found that the deduced alpha values have a strong correlation with the degree of SIA of the quantum wells as predicted theoretically. The good agreement between the theoretical and experimental values of alpha suggests that our WAL approach for deducing alpha values provides a useful tool in designing future spintronics devices that utilize the Rashba spin-orbit coupling.     

Spin-filter device based on the Rashba effect using a nonmagnetic resonant tunneling diode

We propose an electronic spin-filter device that uses a nonmagnetic triple barrier resonant tunneling diode (TB-RTD). This device combines the spin-split resonant tunneling levels induced by the Rashba spin-orbit interaction and the spin blockade phenomena between two regions separated by the middle barrier in the TB-RTD. Detailed calculations using the InAlAs/InGaAs material system reveal that a splitting of a peak should be observed in the I-V curve of this device as a result of the spin-filtering effect. The filtering efficiency exceeds 99.9% at the peak positions in the I-V curve.     

Proton conductivity and microstructures of the core-shell type solid electrolytes in the MO2-In2O3-P2O5 (MTi,Sn, Zr) systems

The proton conducting 0.9MO₂·0.05In₂O₃·1.3P₂O₅ (MTi, Sn, Zr) electrolytes based on a core-shell structure were synthesized by a ball milling method. The core-shell type electrolytes showed the proton conductivities ranging from a higher value than those of Nafion membranes to 10^? 5 Scm^? 1 at intermediate temperatures of 150–200 °C, depending on the heat-treatment conditions. The samples with high conductivity were proved to adopt a core-shell structure by SEM observation, powder XRD analysis and ³¹P MAS-NMR measurements.     

Grassmann manifold of aJH-algebra

We study the set of rankp idempotents in a topologically simple Hilbert Jordan algebra (JH-algebra for short). To produce the differential geometric structure on, we establish Jordan algebraic results concerning the structure of some two-generator subalgebras. We identify geodesics, the Riemannian distance and the sectional curvature of by using the Jordan algebraic structure.     

Electron spin torque in atoms

The spin torque and zeta force, which govern spin dynamics, are studied by using monoatoms in their steady states. We find nonzero local spin torque in transition metal atoms, which is in balance with the counter torque, the zeta force. We show that d-orbital electrons have a crucial effect on these torques. Nonzero local chirality density in transition metal atoms is also found, though the electron mass has the effect to wash out nonzero chirality density. Distribution patterns of the chirality density are the same for Sc–Ni atoms, though the electron density distributions are different.     

Laser ablation synthesis of monodispersed magnetic alloy nanoparticles

Monodispersed CoPt alloy nanoparticles were synthesized by a pulsed laser ablation (PLA) technique coupled with a low-pressure operating differential mobility analyzer (LP-DMA). The CoPt alloy nanoparticles were generated by laser ablating a solid Co–Pt target. In CoPt alloy nanoparticles synthesized from a target with a Co composition of 75 at%, the nanoparticle surfaces were covered by an oxide layer and exhibited a core-shell structure. In contrast, no shell was observed in particles generated from a target with a Co:Pt ratio of 50:50 at%. According to an EDX analysis, the compositions of the individual nanoparticles were almost the same as that of the target material. Finally, the magnetic hysteresis loops of the CoPt alloy nanoparticles exhibited ferromagnetism.