On the accuracy of classical, semiclassical and quantum methods in collision line broadening calculations: Comparative analysis for C2H2-Ar, He systems

Accuracies of classical, semiclassical and quantum methods are comprehensively examined in calculations of impact line widths of C₂H₂ molecules perturbed by Ar and He. The field of comparative study covers both infrared absorption and Raman scattering lines of acetylene having rotational quantum number J=0-30 at temperatures 173 and 296 K. Calculations have been made by fully classical method and by three basic least approximate semiclassical methods, namely, Neilsen-Gordon (NG) method, peaking approximation (PA) and Smith-Giraud-Cooper (SGC) method. Most accurate ab initio potential energy surfaces (PES) of Yang et al. (1996) [21] and Mozsynski et al. (1995) [22] have been applied to model C₂H₂-Ar and C₂H₂-He interactions. The comparison has been made also with available experimental data and with the results of rigorous fully quantum-mechanical calculations within close coupling and coupled states approaches in identical conditions. Semiclassical methods are proved to be not so much accurate as it is generally believed since all they gave in the cases considered seriously underestimated results. The fundamental issue of the adequacy of simplified trajectories in collision broadening calculations is finally reasonably solved. In cases of C₂H₂-Ar and C₂H₂-He systems the use of the “exact” isotropic trajectories (i.e. driven only by the isotropic part of PES) is the main reason of failing of NG, PA and SGC methods. Thus the neglecting of back-influence of the RT exchange on the classical path is a principal defect of semiclassical methods. Finally, the application of simplified trajectories is recognized as inadequate and risky in broadening calculations for molecules having relatively small rotational constants when accurate ab initio PES are applied.     

Silver/polystyrene-coated hollow glass waveguides for the transmission of terahertz radiation

We have applied techniques developed for IR waveguides to fabricate Ag/polystyrene (PS) -coated hollow glass waveguides (HGWs) for transmission of terahertz radiation. A loss of 0.95 dB/m at 119 microm (2.5 THz) was obtained for a 2 mm bore, 90 cm long Ag/PS HGW. We found that TE modes are supported in HGWs with thin PS films, while hybrid (HE) modes dominate when PS film thickness increases. The lowest losses are obtained for the thicker PS films and the propagation of the HE modes.     

Chernoff approximations of Feller semigroups in Riemannian manifolds

Chernoff approximations of Feller semigroups and the associated diffusion processes in Riemannian manifolds are studied. The manifolds are assumed to be of bounded geometry, thus including all compact manifolds and also a wide range of non-compact manifolds. Sufficient conditions are established for a class of second order elliptic operators to generate a Feller semigroup on a (generally non-compact) manifold of bounded geometry. A construction of Chernoff approximations is presented for these Feller semigroups in terms of shift operators. This provides approximations of solutions to initial value problems for parabolic equations with variable coefficients on the manifold. It also yields weak convergence of a sequence of random walks on the manifolds to the diffusion processes associated with the elliptic generator. For parallelizable manifolds this result is applied in particular to the representation of Brownian motion on the manifolds as limits of the corresponding random walks.     

Carleman Estimates for Parabolic Equations with Nonhomogeneous Boundary Conditions

The authors prove a new Carleman estimate for general linear second order parabolic equation with nonhomogeneous boundary conditions. On the basis of this estimate, improved Carleman estimates for the Stokes system and for a system of parabolic equations with a penalty term are obtained. This system can be viewed as an approximation of the Stokes system.     

Sorbents based on transition metal salts for the retention of low molecular weight N-, O- and S-containing organic compounds from the air flow

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Solvent-free silica gel mediated decarboxylation of C–O coupling products of β-diketones and β-oxo esters with malonyl peroxides

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α-Diphenylphosphino-N-(pyrazin-2-yl)glycine as a ligand in Ni-catalyzed ethylene oligomerization

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STEREOSELECTIVE REACTIONS OF CHIRAL AMINES WITH RACEMIC CHLOROPHOSPHINES

Racemic chlorophosphines react stereoselectively with chiral l-phenylethylamines or amino acid esters to give diastereomerically enriched aminophosphines 3, which were isolated as diastereomerically pure crystalline borane complexes. Oxidation, thionation, the reaction with methyl iodide provide optically active derivatives of aminophosphines. (R,S)- and (S,S)-stereomers of phosphinic acid amides were separated by crystallization and a flash-chromatography. The stereochemical properties of phosphorus acid amides were investigated. The mechanism of asymmetric induction at the trivalent phosphorus atom was rationalized.     

Diasteroselective Addition of Monoand Bis-Silylphosphines to Chiral Aldehydes

Abstract

The addition of silylphosphines to chiral aldehydes proceeds with high diastereoselectivity to give optically pure tertiary α -trimethylsiloxyalkylphosphines. The diastereomeric excesses of the addition products were achieved to 90–100%. The reaction of bis(trimethylsilyl)phenylphosphine with the acetonide of (R)-glyceraldehyde provides diastereomerically enriched tertiary bis(glyceryl)phosphines.     

A sensitive chromatographic determination of hydrazines by naphthalene-2,3-dialdehyde derivatization

A new high-performance liquid chromatography (HPLC) method for the sensitive simultaneous determination of hydrazine (Hy), monomethylhydrazine (MMH) and 1,1-dimethylhydrazine (UDMH) based upon the derivatization of hydrazines with naphthalene-2,3-dialdehyde and the separation of the derivatives on Zorbax Eclipse AAA column in a single chromatographic run under acidic conditions (pH 2.4) was developed. Hydrazine and monomethylhydrazine derivatives were found to be strongly fluorescent at λ_ex?=?273?nm, λ_em?=?500?nm. It was shown that UDMH derivative can be detected as non-fluorescent hydrazone at 290?nm by UV-detection. Limits of detection were 0.05?µg?·?L^?1 for Hy and MMH, and 1?µg?·?L^?1 for UDMH for the injection volume of 100?µL. The method was validated for water sample analysis. It proved to be selective, accurate and precise with the supplementary advantage of the simple and rapid sample preparation.