The effect of fluctuations of a classical exterior medium on tunneling nonradiative processes in molecules

We examine nonradiative transitions in molecules with allowance for the effect of a classical polar exterior medium on tunneling charge transport. The approach allows for the vibrational frequencies of a molecule in the electron transition. In the case of slow fluctuations, the theory predicts a low-temperature (non-Arrhenius) increase in the tunneling nonradiative transition rate, and the results agree qualitatively with the experimental data. When the fluctuations of the exterior medium are rapid, at certain values of the molecular parameters the tunneling decay rate is found to decrease with increasing temperature because the conditions needed for resonant tunneling are violated. Zh. éksp. Teor. Fiz. 114, 1944–1953 (December 1998)     

Thickness of a silica-tethered poly(ethylene oxide) layer measured by spin labeling

EPR spectroscopy of labeled poly(ethylene oxide) (PEO) grafted on silica has been used to characterize the conformation and local dynamics of the chains. Grafted molecules of MW 2000 with grafting ratios of 0.045, 0.057, 0.126, and 0.42 molecules/nm² were in contact with benzene. The mobility of the label was compared with that observed for solution of PEO from very diluted to highly concentrated and even bulk PEO. Thus, the concentration inside the grafted layer could be evaluated and also the thickness, which evolves rather linearly with the grafting ratio. © 1995 John Wiley & Sons, Inc.     

Investigation of surface topography, morphology and structure of amorphous carbon films by AFM and TEM

Morphology and structure of amorphous carbon films deposited with a pulsed arc source (LASER-ARC) have been studied using microscopical methods (SEM, TEM and AFM), electron diffraction and spectroscopical investigation (EELS). The parameters of the arc source and the deposition conditions (substrate temperature) influence morphology and structure of deposited amorphous carbon films. Especially the incorporation and growth of particles, embedded in the film have been investigated. By particle analysis using an optical microscope a majority of particles that is smaller than 500 nm has been determined. The morphology has been also demonstrated similar by AFM and TEM images. Their number and size of particles is strongly influenced by the deposition temperature. The structure of amorphous film is characterized by the EELS-spectra, but the particle structure was not detectable.     

A shape model for the twisting power of chiral solutes in nematics

The twisting power of chiral probes in nematics is interpreted in terms of a shape model, in which the surface elements of the solute molecules tend to align with the local director. The theoretical treatment is based on a previous approach, suitable for relating order parameters in nematics to molecular shape, and leads to the definition of a molecular pseudo-tensor whose orientational average determines the pitch and handedness of the helical macrostructures. Results of numerical calculations performed for distorted biphenyl and binaphthyl molecules are in agreement with the experimental results.     

Orientational ordering of liquid crystals containing a difluoro-substituted phenyl ring

The orientational ordering of several liquid crystals containing a difluorosubstituted phenyl ring has been studied through the use of C-13 NMR. The fluorinated phenyl ring of these liquid crystals have C_s symmetry, so three order parameters are required to completely describe the ordering of this ring. All three of these order parameters have been calculated from carbon-fluorine dipolar coupling constants obtained from the carbon-fluorine splittings in the C-13 NMR spectra. Because of the complexity of the fluorine-coupled spectra, variable angle spinning (VAS) was used to resolve the carbon-fluorine splittings. In order to study the orientational ordering over wide ranges of temperature, we have developed an empirical correlation between the order parameter and the value of a carbon-fluorine dipolar coupling constant. This enabled us to study the change in the order parameter with temperature. The results of applying this method to several structurally similar liquid crystals containing the same type of difluorinated phenyl ring are presented. A comparison is made to a similar mono-fluorinated liquid crystal.     

Spectroscopic investigation of Pt—methanol interface in perchloric acid medium by sum-frequency generation

We recorded vibrational spectra of the CO poison resulting from the electrochemical decomposition of CH₃OH on platinum by sum-frequency generation using the infrared free electron laser CLIO. At high CH₃OH concentration (0.1 M) in the electrolyte, both multi-bonded and linearly bonded CO are equally present. At lower CH₃OH concentration (0.004 M), the multi-bonded species is predominant. The CO poison still remains on the surface at potentials (0.05 V/NHE) close to the hydrogen evolution onset.     

Advanced in the synthesis of heterocyclic compounds from aliphatic nitro derivatives. A review

The literature on the synthesis of heterocyclic compounds from aliphatic nitro derivatives in the past decade has been summarized.Moscow State Textile Academy, 117918, Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1299–1336, October, 1994. Original article submitted October 6, 1994.     

Lattices of processes for graphs

The structure of the lattice of processes of a finite digraph with entries is investigated. Necessary and sufficient conditions for the isomorphism of a given lattice to the lattice of processes of a certain digraph are obtained. Bibliography: 5 titles. Translated by K. V. Shakhbazyan. Translated fromZapiski Nauchnykh Seminarov POMI, Vol. 202, 1992, pp. 135–153.     

Intermittency for coherent and incoherent current ensemble model

We investigate the origin of intermittency for multiparticle distribution in momentum space, following the idea that there is a kind of power law distribution of the space-time region of hadron emission. Using the formalism of current ensamble model to describe boson sources we discuss intermittency exponents for the coherent and incoherent (chaotic) particle production scheme.     

Thermally stimulated current and DSC studies of the broadened glass transition in liquid crystalline polymers

The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main T_g, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that T_g is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc.