Adiabatic photodissociation of acenaphthylene dimers in the excited singlet state

Fluorescence spectroscopic studies of acenaphthylene dimers in saturated hydrocarbon solution have revealed that the dimer (A₂) photodissociates to     

Spectral Analysis of Stochastic Phase Lockings and Stochastic Bifurcations in the Sinusoidally Forced van der Pol Oscillator with Additive Noise

Noise effects on the phase lockings and bifurcations in the sinusoidally forced van der Pol relaxation oscillator are investigated. Deterministic (noise-free) one-dimensional Poincaré mapping is extended to the iteration of the operator defined by a stochastic kernel function. Stochastic phase lockings and bifurcations are analyzed in terms of the density evolution by the operator. In particular, a new method which uses spectra (eigenvalues and eigenfunctions) of the operator to analyze stochastic bifurcations intensively is proposed.     

Kinetics and mechanism of the autoxidation of pentaerythrityl tetraheptanoate at 180–220°C

A kinetic and mechanistic study of the autoxidation of liquid pentaerythrityl tetraheptanoate (PETH) at 180–220°C has been carried out utilizing a stirred-flow reactor. The results are consistent with the occurrence of a chain reaction scheme similar to that proposed for n-hexadecane autoxidation, namely, the formation of monohydroperoxides by the intermolecular abstraction reaction (3), the formation of α,γ- and α,δ-dihydroperoxides and α,γ- and α,δ-hydroperoxyketones by intramolecular peroxy radical abstraction reactions (4) and (4*), the bimolecular termination of peroxy radicals, reaction (6), and the rapid conversion of α,γ-hydroperoxyketones to the corresponding cleavage acids and methyl ketones, reaction (7). Comparisons of various rate parameters for the n-hexadecane and PETH systems reveal that the values of k₇ and (k₃/H atom)/(2 k₆)^1/2 are within experimental uncertainties identical for the two systems at 180°C. The proposed reaction scheme includes the concurrent formation of hydroxy radicals and hydroperoxyketone species. The results of kinetic analysis and the experimentally observed isomer distributions of primary and secondary monohydroperoxide products at high and low oxygen pressures suggest that ≈60% of the hydrogen abstractions from PETH at high oxygen pressures occur by hydroxy radicals.     

Synthesis of pyrochlore tungsten trioxide thin film and electrochemical lithium intercalation

The pyrochlore tungstate thin film has been prepared by an autoclave hydrothermal method at a temperature of 200 °C. The film was characterized by X-ray diffractometry, X-ray photoelectron spectroscopy and scanning electron micrograph measurements, showing that pure pyrochlore phase of sodium tungstate containing a small amount of water was formed by heating the film at a temperature of 350 °C. The cyclic voltammetric and galvanostic measurements revealed that a reversible electrochemical lithium intercalation into the crystal lattice of pyrochlore tungstate film takes place with charge-discharge cycling. Furthermore, the thermodynamics and kinetics of electrochemical lithium intercalation into the pyrochlore sodium tungstate film were also studied.     

Low-temperature elastic moduli and internal dilational and shear friction of polymethyl methacrylate

Longitudinal and transverse wave velocity, five kinds of elastic parameters (young, shear and bulk moduli, Lamér; parameter. Poisson's ratio) and dilational and shear internal friction of polymethyl methacrylate were simultaneously measured over a temperature range 68–400K, using the ultrasonic pulse method. All elastic moduli decrease with increasing temperature, suggesting lowering of molecular bonding strength. From dilational and shear internal frictions, the 139, 382, and 385K peaks are interpreted as rotation of x-methyl estel groups, micro Brownian motion of main chains and stress relaxation, and abrupt increases from 242 and 395K are regarded as free motion of side chains and glass transition, respectively. ©1995 John Wiley & Sons, Inc.     

Effect of the 16O → 18O isotopic substitution and a magnetic field on the spin dynamics in the (La0.25Pr0.75)0.7Ca0.3MnO3 manganite according to the 139La NMR data

¹³⁹La nuclear magnetic resonance spectra have been recorded and the spin-spin relaxation times in the paramagnetic region in external magnetic fields of 5 and 9.4 T have been measured for two types of manganites: initial (La_0.25Pr_0.75)_0.7Ca_0.3Mn¹⁶O₃ and enriched with the ¹⁸O isotope ((La_0.25Pr_0.75)_0.7Ca_0.3Mn¹⁸O₃). The manganite enriched with the heavier oxygen isotope exhibits disappearance of a signal in the charge-ordering region (T < T _co) in an external field of 5 T. This effect is related to the anomalous increase in the spin-spin relaxation rate. With an increase in the external magnetic field to 9.4 T, the difference in the behavior of the relaxation rate for the two samples in the charge-ordering region remains pronounced, although the magnitude of this effect becomes much smaller. The observed giant isotope effect is a bright evidence of the important role of oxygen motion in the formation of long-range magnetic order in the manganites under consideration. Original Russian Text ? K.N. Mikhalev, I.E. Litvinov, Z.N. Nigamat’yanova, A.Yu. Yakubovskii, A.R. Kaul’, O.Yu. Gorbenko, K. Kumagai, Y. Furukawa, 2007, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2007, Vol. 71, No. 5, pp. 726–729.     

Heat kernel estimates for FIN processes associated with resistance forms

Quenched and annealed heat kernel estimates are established for Fontes–Isopi–Newman (FIN) processes on spaces equipped with a resistance form. These results are new even in the case of the one-dimensional FIN diffusion, and also apply to fractals such as the Sierpinski gasket and carpet.