Isotopic effects in H-atom abstraction from matrix molecules by methyl radicals in poly(methyl methacrylate). Determination of the scale of relative reagent motions

The H-abstraction by ?H₃ and ?D₃ radicals from PMMA molecules is investigated at 77 and 120 K. The film samples are prepared from the mixture of normal and deuterated PMMA. The reaction is of the first order with respect to radical concentration. Its rate is retarded in time as compared to the exponential law. An analysis of the molecular product ratio for the reaction allows the primary isotopic effect to be estimated. The initial reaction rate depends nonmonotonously on the proportion of the deuterated polymer in the matrix. Namely, there exists a range of isotopic compositions, with the reaction rate increasing with the portion of a deuteropolymer in the mixture. At 77 K the reaction rate of ?D₃ is lower than that of ?H₃ in PMMA of a mixed isotopic composition. This results from the proximity of ?D₃ with unreactive parental macromolecules, which reduces the local H concentrations around ?D₃ as compared to the mean concentration. At 120 K the radical decay rates do not differ. This fact cannot be explained by unfrozen mobilities of radicals at high temperatures or by their migration from parental macromolecules. The phenomenon is interpreted in terms of thermal fluctuations involving a great area around a radical and ensuring its migration within this area. The electron spin echo method is used to estimate the distance between a radical and its parental macromolecule, a ≥ 9.6 Å. This is the lower limit of the reaction accessibility.     

Electronic spectra of cationic forms of meso-tetrapropylporphin in a nanoporous silicate gel matrix

We have studied the fluorescence and fluorescence excitation spectra at 300 K, 77 K, and 4.2 K for silicate gel matrices colored with meso-tetrapropylporphin by impregnation of the matrix with a solution of the pigment. Comparison of the data obtained with the absorption spectra in acidified solutions and analysis of the low-temperature fine-structure vibronic spectra, and also taking into account data obtained earlier for octaethylporphin in a xerogel showed formation of two cationic forms of meso-tetrapropylporphin in the gel matrix: the short-wavelength form has a dicationic structure, while the long-wavelength form has a monocationic structure. We have traced out the correlations of the vibrational structure in the spectra of the dicationic form with data for the porphin dication, and we have drawn a number of conclusions concerning the normal vibrational modes that are active in the vibronic fluorescence and absorption spectra of the studied cationic forms. Using the AM1 semiempirical quantum chemical method, we optimized the geometry of the mesotetrapropylporphin dication: the most stable of the possible conformers is the dication structure with saddleshaped macrocycle nonplanarity. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 453–461, July–August, 2006.     

Ion synthesis and laser annealing of Cu nanoparticles in Al2O3

Al₂O₃ samples with Cu nanoparticles, synthesised by ion implantation at 40 keV with a dose of 1×10¹⁷ ion/cm² and a current density from 2.5 to 12.5 μA/cm², were annealed using ten pulses from a KrF excimer laser with a single pulse fluence of 0.3 J/cm². The copper depth distribution, formation and modification of metal nanoparticles under the ion implantation and laser treatment were studied by Rutherford backscattering (RBS), energy dispersive X-ray (EDX) analysis, atomic force microscopy (AFM) and optical spectroscopy. It was found that laser annealing leads to a reduction in the nanoparticle size without diffusion of metal atoms into the bulk. The change in particle size and the possibility for oxidation of the copper particles are examined in the framework of Mie theory. Calculations presented show that under excimer laser treatment, Cu nanoparticles are more likely to be reduced in size than to undergo oxidation. Received: 19 April 2001 / Accepted: 7 November 2001 / Published online: 23 January 2002     

Pomeron-Odderon interference effects in electroproduction of two pions

We study Pomeron-Odderon interference effects giving rise to charge and single-spin asymmetries in diffractive electroproduction of a pair. We calculate these asymmetries, originating from both longitudinal and transverse polarizations of the virtual photon, in the framework of QCD and in the Born approximation, in a kinematical domain accessible to HERA experiments. We predict a sizable charge asymmetry with a characteristic dependence on the invariant mass of the pair, which makes this observable very important for establishing the magnitude of the Odderon exchange in hard processes. The single-spin asymmetry turns out to be rather small. We briefly discuss future improvements of our calculations and their possible effects on the results. Received: 18 July 2002 / Published online: 25 October 2002     

Cardy's formula for some dependent percolation models

We prove Cardy's formula for rectangular crossing probabilities in dependent site percolation models that arise from a deterministic cellular automaton with a random initial state. The cellular automaton corresponds to the zero-temperature case of Domany's stochastic Ising ferromagnet on the hexagonal lattice  (with alternating updates of two sublattices) [7]; it may also be realized on the triangular lattice 𝕋 with flips when a site disagrees with six, five and sometimes four of its six neighbors. Received: 24 December 2001     

Illusions of vision: Interpretation within the framework of a holographic model

Several illusions of vision are considered on the basis of a neurophysiological holographic model of visual perception at the level of the eye’s and the retina. It is suggested that the eye’s optical system forms a spatial spectrum of the observed object rather than its image on the retina. The spectrum is encoded by active anisotropic quasi-crystalline structures of rod rhodopsins and cone iodopsins, and a complex Fourier hologram of the observed object consisting of two quadrature components is recorded. The holographic hypothesis is confirmed by the results obtained by digital simulation.