Nonlinear Theory of Spectra of Thermally Stimulated Currents in Complex Crystals with Hydrogen Bonds

The nonlinear theory of thermally stimulated depolarization currents is developed. The theory explains the processes of hetero- and homocharge relaxation in complex crystals with hydrogen bonds and allows the relaxation oscillator parameters to be calculated using the quadratic approximation for the external electric field.     

Conformational analysis of dipeptide‐derived polyisocyanides

The conformational properties of polymers derived from isocyanodipeptides have been investigated with a combination of model calculations, X‐ray diffraction, and circular dichroism spectroscopy. Depending on the configuration of the side chains, defined arrays of hydrogen bonds along the polymeric backbone are formed. This leads to a well‐defined conformation as, for example, expressed in the formation of lyotropic liquid‐crystalline phases and increased helical stability. Upon the disruption of the hydrogen bonds by a strong acid, a less well‐defined macromolecular conformation is observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1725–1736, 2003     

Nonequilibrium Ionization by Vibrationally Excited Molecules in Supersonic Flows

The results of experimental investigations on thermal nonequilibrium ionization in CO₂: N₂: He mixtures are presented. Measurements of electron density, n_e, in vibrationally excited nitrogen were made in a supersonic flow with different CO₂ contents as well as in a CO₂: N₂: He = 1 : 5 : 4 mixture laser gas. The mixtures were heated in a shock tube and expanded through a supersonic nozzle. Furthermore, supersonic mixing of N₂ and CO₂ + He was used in some experiments. The measured values of n_e in the plenum chamber and in the supersonic nozzle are reported, and the processes responsible for nonequilibrium ionization in a laser-active medium are discussed.     

Explicit Formulas for Generalized Action–Angle Variables in a Neighborhood of an Isotropic Torus and Their Application

Different versions of the Darboux–Weinstein theorem guarantee the existence of action–angle-type variables and the harmonic-oscillator variables in a neighborhood of isotropic tori in the phase space. The procedure for constructing these variables is reduced to solving a rather complicated system of partial differential equations. We show that this system can be integrated in quadratures, which permits reducing the problem of constructing these variables to solving a system of quadratic equations. We discuss several applications of this purely geometric fact in problems of classical and quantum mechanics.     

Rate constants for the gas‐phase reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals at 250–430 K

The rate constants k₁ for the reaction of CF₃CF₂CF₂CF₂CF₂CHF₂ with OH radicals were determined by using both absolute and relative rate methods. The absolute rate constants were measured at 250–430 K using the flash photolysis–laser‐induced fluorescence (FP‐LIF) technique and the laser photolysis–laser‐induced fluorescence (LP‐LIF) technique to monitor the OH radical concentration. The relative rate constants were measured at 253–328 K in an 11.5‐dm³ reaction chamber with either CHF₂Cl or CH₂FCF₃ as a reference compound. OH radicals were produced by UV photolysis of an O₃–H₂O–He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during the UV irradiation. The k₁ (298 K) values determined by the absolute method were (1.69 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (FP‐LIF method) and (1.72 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (LP‐LIF method), whereas the K₁ (298 K) values determined by the relative method were (1.87 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CHF₂Cl reference) and (2.12 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CH₂FCF₃ reference). These data are in agreement with each other within the estimated experimental uncertainties. The Arrhenius rate constant determined from the kinetic data was K₁ = (4.71 ± 0.94) × 10^?13 exp[?(1630 ± 80)/T] cm³ molecule^?1 s^?1. Using kinetic data for the reaction of tropospheric CH₃CCl₃ with OH radicals [k₁ (272 K) = 6.0 × 10^?15 cm³ molecule^?1 s^?1, tropospheric lifetime of CH₃CCl₃ = 6.0 years], we estimated the tropospheric lifetime of CF₃CF₂CF₂CF₂CF₂CHF₂ through reaction with OH radicals to be 31 years. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 26–33, 2004     

Naphthyl azomesogens with lateral chloro groups

A homologous series of azomesogens, 2″-[4-(4′-n-alkoxybenzoyloxy)-2-chlorophenylazo] naphthalenes, with lateral chloro groups was synthesised. All the homologues synthesized exhibit enantiotropic nematic mesophase. The mesomorphic properties of the present series are compared with other structurally related series to evaluate the effect of lateral chloro group and its position on mesomorphism This paper was presented at the 10th National Conference on Liquid Crystals held at Bangalore, India during 9–11 October 2003.     

Cochran's statistical theorem for outer inverses of matrices and matrix quadratic forms

We extend the matrix version of Cochran's statistical theorem to outer inverses of a matrix. As applications, we investigate the Wishartness and independence of matrix quadratic forms for Kronecker product covariance structures.