Generalized characterization of relaxation properties and high elasticity of polymeric systems

Measurements of apparent viscosity, normal stress coefficient, and storage and loss moduli have been used to determine the characteristic relaxation time. The ratio of the characteristic relaxation time θ_in corresponding to a given deformation rate ˙γ to that of the initial state θ_e is found to be a function of ˙γθ_in. For a wide range of polymeric systems, the ratio of normal stress to the initial high elasticity modulus and to the high elastic deformation γ_e are the same function of ˙γθ_in. It has been established that γ_e, like other viscoelastic characteristics of polymer systems, is determined by the relaxation properties and their variation due to deformation. The dependence of γ_e on θ_e/θ_in is common to a wide range of polymeric systems. The generalized characteristics were independent of the nature of the polymeric chain, molecular weight, molecular weight distribution, temperature, polymer concentration in solution, and solvent type. These results allow us to describe approximately normal stresses and high-elastic deformations as functions of shear rate and storage and loss moduli as functions of frequency, if we know θ_in the relation between shearing stress and shear rate.     

The origin of luminescence accompanying electrochemical reduction or chemical decomposition of peroxydisulfates

The spectral features of the electrochemiluminescence occurring during the reduction of peroxydisulfate anions at magnesium, silver or platinum electrodes (ecl), the luminescence following their decomposition on a magnesium surface (mcl), and the chemiluminescence accompanying the thermal decomposition of peroxydisulfates in acidic media (tcl), were thoroughly examined in order to discover the origin of the light emission. The intensity of emission followed the order ecl>mcl?tcl and depended on the method of its generation and other experimental conditions. Probable pathways of the reactions leading to the formation of light-emitting species were examined at the density functional theory level. The theoretical studies and experimental findings seem to indicate that the luminescence originates from ¹O₂, ¹(O₂)₂ and ³(O₂)₂, the precursors of which are SO₄^•−, HO^•, HOO^•, HOOH and O₃ formed in the primary and secondary processes following electrochemical reduction or thermal decomposition of peroxydisulfates. Supplementary experiments demonstrated the participation of HOOH in the generation of light emitting entities.     

Anisotropic pressure in dense neutron matter under the presence of a strong magnetic field

Dense neutron matter with recently developed BSk19 and BSk21 Skyrme effective forces is considered in magnetic fields up to ¹⁰²⁰ G at zero temperature. The breaking of the rotational symmetry by the magnetic field leads to the differentiation between the pressures along and perpendicular to the field direction which becomes significant in the fields H>Hth∼¹⁰¹⁸ G. The longitudinal pressure vanishes in the critical field ¹⁰¹⁸<Hc?¹⁰¹⁹ G, resulting in the longitudinal instability of neutron matter. For the Skyrme force fitted to the stiffer underlying equation of state (BSk21 vs. BSk19) the threshold Hth and critical Hc magnetic fields become larger. The longitudinal and transverse pressures as well as the anisotropic equation of state of neutron matter are determined under the conditions relevant for the cores of magnetars.     

Effect of solvation on the vertical ionization energy of thymine: from microhydration to bulk

The effect of hydration on the vertical ionization energy (VIE) of thymine was characterized using equation-of-motion ionization potential coupled-cluster (EOM-IP-CCSD) and effective fragment potential (EFP) methods. We considered several microsolvated clusters as well as thymine solvated in bulk water. The VIE in bulk water was computed by averaging over solvent-solute configurations obtained from equilibrium molecular dynamics trajectories at 300 K. The effect of microsolvation was analyzed and contrasted against the combined effect of the first solvation shell in bulk water. Microsolvation reduces the ionization energy (IE) by about 0.1 eV per water molecule, while the first solvation shell increases the IE by 0.1 eV. The subsequent solvation lowers the IE, and the bulk value of the solvent-induced shift of thymine's VIE is approximately -0.9 eV. The combined effect of the first solvation shell was explained in terms of specific solute-solvent interactions, which were investigated using model structures. The convergence of IE to the bulk value requires the hydration sphere of approximately 13.5 ? radius. The performance of the EOM-IP-CCSD/EFP scheme was benchmarked against full EOM-IP-CCSD using microhydrated structures. The errors were found to be less than 0.01-0.02 eV. The relative importance of the polarization and higher multipole moments in EFP model was also investigated.     

Shape and location of multiple charge carriers in linear π‐electron systems

We have performed a quantum‐mechanical study of a series of neutral polyenes, their multiply charged ions, and related ionic polymethines with a closed electron shell, using different methods/basis with/without electron correlations. The study shows that a multiple injection of charge carriers into a collective system of π‐electrons causes a formation of distinctive electron levels in the energy gap along with a simultaneous regular gap shift in accordance to the number of injected carriers. Each charge generates its own solitonic electron density alternation wave on adjacent carbon atoms, as well as similar bond length and valence angle alternation waves. Established regularities in charge distribution and variations of bond lengths and valence angles may be used in the molecular design of organic semiconducting materials. © 2013 Wiley Periodicals, Inc.     

Rheology of silica-filled polystyrene: From microcomposites to nanocomposites

Rheology and viscoelastic behavior of polystyrene (PS)/silica microcomposites and nanocomposites were studied. The apparent viscosity, transient shear stress growth after startup shear flow and stress relaxation after cessation of flow at various shear rates, the complex dynamic viscosity, the storage and loss moduli at small and large strain amplitudes and various frequencies were performed. The effect of size, shape and volume concentration of silica was discussed. The maximum volume concentration, corresponding to the concentration at which the relative viscosity of mixtures goes to infinity, with respect to the hydrodynamic contribution of the particles and to polymer-filler interactions was obtained. The difference between the yield stress and residual stress is shown. The domain of equivalence between the apparent viscosity as a function of the shear rate in steady state flow and the complex dynamic viscosity as a function of the strain rate amplitude in highly nonlinear region of oscillatory flow was established. The viscoelastic behavior was interpreted based on the morphology of microcomposites and nanocomposites observed by SEM.     

A lattice approach to narrow operators

It is known that if a rearrangement invariant function space E on [0,1] has an unconditional basis then each linear continuous operator on E is a sum of two narrow operators. On the other hand, the sum of two narrow operators in L₁ is narrow. To find a general approach to these results, we extend the notion of a narrow operator to the case when the domain space is a vector lattice. Our main result asserts that the set N_r(E, F) of all narrow regular operators is a band in the vector lattice L_r(E, F) of all regular operators from a non-atomic order continuous Banach lattice E to an order continuous Banach lattice F. The band generated by the disjointness preserving operators is the orthogonal complement to N_r(E, F) in L_r(E, F). As a consequence we obtain the following generalization of the Kalton-Rosenthal theorem: every regular operator T : E → F from a non-atomic Banach lattice E to an order continuous Banach lattice F has a unique representation as T = T_D + T_N where T_D is a sum of an order absolutely summable family of disjointness preserving operators and T_N is narrow. Supported by Ukr. Derzh. Tema N 0103Y001103.