The effect of spin-orbit coupling on fast neutral chemical reaction O(3P)+CH3-->CH3O

The effect of nonadiabatic transitions through the spin-orbit couplings has been investigated on the fast neutral reaction, O((3)P)+CH(3)-->CH(3)O. Adiabatic potential energies and the spin-orbit coupling terms have been evaluated for the four electronic states of CH(3)O ((2)E, (2)A(2), (4)E, and (4)A(2)) that correlate with the O((3)P)+CH(3) asymptote, as a function of CO distance and OCH angle under the C(3v) symmetry, by ab initio electronic structure calculations using multireference internally contracted single and double excitation configuration interaction method with the 6-311G(2df,2pd) basis sets. Multistate quantum reactive scattering calculations have been carried out with the use of thus obtained potential energies and spin-orbit coupling matrices, based on the generalized R-matrix propagation method. The calculated thermal rate constants show a slight positive dependence on temperature in a range between 50 and 2000 K, supporting the previous experimental results. It is shown that the spin-orbit coupled excited states give rise to reflections over the centrifugal barrier due to the quantum interference. Classical capture calculations yield larger rate constants due to the neglect of quantum reflections. It is concluded that the effect of nonadiabatic transitions is of minor importance on the overall reactivity in this reaction.     

Photoassisted oxygenation of alkane catalyzed by ruthenium complexes using 2,6-dichloropyridine N-oxide under visible light irradiation

The chloro(Me(2)SO)ruthenium(II) complexes with tris(2-pyridylmethyl)amine or its derivative catalyses the selective, stereospecific, and photoregulative alkane oxidation in the presence of 2,6-dichloropyridine N-oxide under visible light irradiation.     

Behavior of nitroxyl radical in the polymerization process forming copolymers bearing diarylnitrone pendants and photocontrol of refractive indices for these copolymers

To establish the reaction condition under which the radical copolymerization of methyl methacrylate (MMA) with α‐(2‐hydroxy‐4‐methacryloyloxyphenyl)‐N‐(2,6‐dimethylphenyl)nitrone (HMDN) proceeds smoothly to give photoreactive copolymers, the effects of the nitrone chromophore on the extent to which the radical polymerization of MMA is inhibited were investigated. It was found that the reversible addition of initiating radical to the CH?N⁺(? O^?) moiety in the nitrone chromophore readily occurs to give the nitroxyl radical. It was also found that the latter radical undergoes an efficient coupling reaction with propagating radical to inhibit the radical copolymerization of MMA with HMDN. However, on raising the reaction temperature and the radical concentration, the copolymerization was successfully carried out. This polymerization condition allowed us to prepare the HMDN/MMA, HMDN/styrene, and HMDN/cyclohexyl acrylate copolymers in good yields. The photoirradiation of the copolymer film prepared on a silicon wafer lowered its refractive index by 0.003–0.023, depending on the relative composition of the diarylnitrone chromophore in these copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 88–97, 2006     

Collapse of thermal activation in moderately damped Josephson junctions

We study switching current statistics in moderately damped Nb-InAs-Nb and intrinsic Bi2Sr2CaCu2O8+delta) Josephson junctions. A paradoxical collapse of thermal activation with increasing temperature is reported and explained by the interplay of two conflicting consequences of thermal fluctuations, which can both assist in premature escape and help in retrapping back into the stationary state. We analyze the influence of dissipation on the thermal escape by tuning damping with a gate voltage, magnetic field, temperature, and an in situ capacitor.     

UHV transmission electron microscopy on the reconstructed surface of (111) gold: I. General features

The reconstructed surface structure of (111) gold was studied by ultra-high vacuum transmission electron microscopy and diffraction and the results are described in this series of papers. In part I the observed fringes spaced about 6.3 nm in the images of (111) gold platelets grown on molybdenite, magnesium oxide and graphite are shown to be due to a reconstructed surface structure of unidirectional shrinkage of the surface layer by about 4% along one of the 〈1$\text{1}$0〉 directions on the (111) surface. The shrinkage of the surface layer of the same amount from the bulk lattice was found to take place on gold crystals of different lattice parameters, which were formed by pseudomorphic overgrowth of gold on gold containing various amounts of palladium and indium. Evidence is given for the fact that the shrinkage is not uniform and the observed fringes are not simple interference fringes between the shrunk surface layer and the underlying bulk lattice. At high temperatures the structure first transforms gradually and reversibly to an isotropically shrunk one, and finally the reconstruction disappears above about 900°C.     

Morphological effects on formation and behavior of radicals in γ-irradiated polyethylene single crystals

Polyethylene single crystals differing in lamellar thickness, both as-grown and annealed with different lamellar thickness, were irradiated by γ-rays to a dose of about 10⁷ rad at liquid nitrogen temperature in vacuo, and then ESR measurements were made. It was found for the as-grown crystals that alkyl radicals were concentrated at the crystal surface. For the annealed crystals it was found that the radical concentration was greater than in the original crystals because of an increase in disorder with annealing. By assuming that the crystals form blocks upon annealing and that the surface and the interior of the blocks have the same trapping capacities for radicals as in the original crystals, the dependence of the size of the blocks upon variation in annealing temperature and the original lamellar thickness was estimated. This estimate is supported by the theory of the thickening process of single crystals. Two types of radical reactions with different reaction rates were found to occur simultaneously at room temperature. The rapid process was independent of lamellar thickness and was related to the reaction of radicals mainly in the surface region and the defects within the crystals. The slow process was strongly dependent on the lamellar thickness (i.e., the reaction rate was much depressed as the lamellar thickness was increased) and was inferred to be closely related to molecular motions manifested in viscoelastic measurements by the crystalline dispersion α_c.     

Ultra-high-vacuum in situ electron microscopy of growth processes of epitaxial thin films

Extracts from recent results of ultra-high-vacuum in-situ electron microscopy of growth processes of epitaxial thin films are given. As a modified monolayer-by-monolayer mode, the growth process in Fe/(111)Au of the initial Frank-van der Merwe type, followed by the intrinsic γ → α transformation of Fe is mentioned. For the nucleation and growth mode, a systematic selection of epitaxial orientation according to interfacial lattice fitting, nucleation and coalescence features, the validity of Cabrera's suggestion extending Frank and van der Merwe's idea, the cluster mobility and effects of grown-in dislocations in substrate crystals are discussed on the basis of the observations.