Superradiating 4P-4S-3P cascade of sodium vapour arising on the leading edge of the exciting laser pulse

Investigations of the superradiating cascade of sodium vapour 4P-4S-3P ₁ = 2.21 µm and ₂=1.14 µm) arising on the leading edge of the exciting laser pulse were carried out. The dependences of the actual delay time _D of the ₁ pulse on the population rise time of the laser-excited 4P state were measured and compared with those calculated following the existing theoretical model. The dependence of the actual delay time _D on the inverse density of excited atoms 1/N* is also presented. Analysis of this dependence revealed the influence of the Doppler dephasing and of the second, ₂, transition on the formation of the ₁ superradiance.     

On the electrostatic and steric similarity of lactam compounds and the natural substrate for bacterial cell-wall biosynthesis

Summary Electrostatic and structural properties of a set of -lactam, -lactam and nonlactam compounds have been analyzed and compared with those of a model of the natural substrate d-alanyl-d-alanine for the carboxy- and transpeptidase enzymes. This first comparison of the electrostatic properties has been based on a distributed multipole analysis of high-quality ab initio wave functions of the substrate and potential antibiotics. The electrostatic similarity of the substrate and active compounds is apparent, and contrasts with the electrostatic properties of the noninhibitors. This has been quantified to give a reasonable correlation with the MIC (Minimum Concentration for Inhibition) and with kinetic data (k₂/K) in accordance with the model for interaction of the lactam compounds with dd-peptidase. These correlations provide a better prediction of antibacterial activity than purely structural criteria.     

Sensitivity analysis of the greatest eigenvalue of a symmetric matrix via the ɛ-subdifferential of the associated convex quadratic form

LetA(·) be ann × n symmetric affine matrix-valued function of a parameteruR ^m , and let (u) be the greatest eigenvalue ofA(u). Recently, there has been interest in calculating (u), the subdifferential of atu, which is useful for both the construction of efficient algorithms for the minimization of (u) and the sensitivity analysis of (u), namely, the perturbation theory of (u). In this paper, more generally, we investigate the Legendre-Fenchel conjugate function of (·) and the -subdifferential (u) of atu. Then, we discuss relations between the set (u) and some perturbation bounds for (u).The author is deeply indebted to Professor J. B. Hiriart-Urruty who suggested this study and provided helpful advice and constant encouragement. The author also thanks the referees and the editors for their substantial help in the improvement of this paper.     

A large deviation principle for (r,p)-capacities on the Wiener space

Summary We formulate and prove a large deviation principle for the (r, p)-capacity on an abstract Wiener space. As an application, we obtain a sharpening of Strassen's law of the iterated logarithm in terms of the capacity.     

Spin density distributions in radical anions of heterocyclic amine N-oxides

The unrestricted Hartree-Fock (UHF) method of Snyder and Amos is used to calculate, in the -electron approximation, the spin density distributions in radical anions of heterocyclic amine N-oxides. The computed spin densities are observed to be in good agreement with the experimental values. The computed spin density distribution of the radical anion of pyridine N-oxide is consistent with the greater susceptibility of pyridine N-oxide relative to pyridine to electrophilic nitration. Also, the calculations are consistent with the lower basicity of the N-oxides relative to the parent bases.     

Spectrophotometric determination of Fe(II) in milligram solid samples

The analytical procedure of determination of Fe(II) in the presence of Fe(III) in milligram samples is proposed. A solid sample is dissolved in hydrochloric acid in argon atmosphere. Subsequently, the pH-value of the solution is fixed and Fe(III) complexed by phosphoric buffer. At the next step Fe(II) is oxidized by -molybdosilicic acid. Finally, the intensity of colouring caused by the reduced form of the acid is measured at the wavelength 770 nm. The proper treatment of the sample during oxidation, and immediately before, is decisive for the accuracy of the analysis. The method was verified by means of the analysis of synthetic magnetite. The theoretical content of Fe(II) was 24.12%, the determined one was 24.02 ± 0.10%. The method was applied to the determination of the homogeneity of an iron catalyst for ammonia synthesis.     

Chemical applications of group theory and topology

The following procedure is described for investigating the qualitative dynamics of simple chemical systems: 1) A so-called influence diagram is generated representing the relationships between the reference reactants (phase-determining intermediates); 2) This influence diagram is used to generate a truth table indicating possible transitions between state vectors representing the signs of the time derivatives of of the reference reactant concentrations; 3) The truth table is used to determine a state transition diagram representing the flow topology around unstable equilibrium points; 4) The characteristic equation of the adjacency matrix of the influence diagram is solved in order to determine the presence of such unstable equilibrium points. The two types of qualitative dynamics possible for chemical systems containing two reference reactants and one feedback circuit are bifurcation between two attracting regions (bistability) and limit cycle oscillation. However, in two reference reactant systems oscillation requires an additional self-activating loop to generate the unstable equilibrium point required for its realization. Bistability and limit cycle oscillation are also two of the possible types of qualitative dynamics for chemical systems containing three reference reactants. However, chemical systems with three reference reactants and two or more feedback circuits can also contain interlocking limit cycles, which can lead to toroidal oscillations or chaos. The influence diagrams are given for the systems exhibiting these various types of dynamic behavior along with a summary of the important properties of all 729 possible influences for simple chemical systems containing three reference reactants.     

The inclusion complex of piromidic acid with dimethyl-β-cyclodextrin in aqueous solution and in the solid state

Inclusion complex formation of piromidic acid (PA) with dimethyl--cyclodextrin (DM--CD) in aqueous solution and in the solid state was confirmed by the solubility method, differential scanning calorimetry (DSC) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy. The apparent stability constant,K _c , of the complex was estimated to be 244 M^–1. The stoichiometry of the complex was given as the ratio 1:2 of PA to DM--CD. The dissolution rate of the PA/DM--CD complex was much greater than that of intact PA.Presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on Cyclodextrins, Lancaster, U.K., 20–25 July 1986.     

Ab initio calculation of 4-ClC6H4CH2Cl and peculiarities of electron density distribution in this molecule

Ab initio calculation of the 4-ClC₆H₄CH₂Cl molecule was performed by the restricted Hartree-Fock method in the split valence 6–31 G* basis set with complete optimization of its geometry. Populations of p-orbitals of atoms of this molecule were analyzed.³⁵Cl NQR frequencies and asymmetry parameters of the electric field gradient on³⁵Cl nuclei were estimated on the basis of the populations of valent p-orbitals of CI atoms and their components. Good conformity with the experimental values was obtained when only less diffuse components of p-orbitals were used in calculations of populations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 823–826, April, 1996.     

Delocalization corrections to the strictly localized molecular orbitals: A linearized SCF approximation

An explicit formula is derived for calculating the delocalization corrections (tails) to be added to the strictly localized bond orbitals. It was obtained by solving analytically the SCF problem for the interbond interactions in a linearized approximation. The model calculations at the CNDO/2 level show that this simple approach is sufficient to account for the molecular conformations.