On Some Properties of Bilinear Maps of Order Bounded Variation

In this paper we study properties of bilinear maps of order bounded variation. Theorems of preservation of properties in passage to the triadjoint and the tensor product are presented.     

Ground and excited state CASPT2 geometry optimizations of small organic molecules

A method for computing second-order multiconfigurational perturbation theory (CASPT2) energy gradients numerically has been implemented and applied to a range of elementary organic chromophores, including 1,3 butadiene, acrolein, and two protonated Schiff bases. Geometries of ground and excited states-as well as conical intersections-are compared with the corresponding CASSCF structures, illustrating the effect of including the correction for dynamical electron correlation. It is shown that the differences between the two methods are not readily categorized, but that, while individual changes in bond lengths can be quite large ( approximately 0.01-0.02 A), the natures and CASPT2 energetics of the structures remain similar. Exceptions to this tend to be systems that have a strong ionic character and that are not well described at the CASSCF level. Basis set effects (double- vs. triple-zeta) were examined for a limited number of examples, and found to be quite dramatic at both levels of theory.     

Structure-reactivity relationships in the inactivation of elastase by beta-sultams

N-Acyl-beta-sultams are time dependent irreversible active site directed inhibitors of elastase. The rate of inactivation is first order with respect to beta-sultam concentration and the second order rate constants show a similar dependence on pH to that for the hydrolysis of a peptide substrate. Inactivation is due to the formation of a stable 1:1 enzyme inhibitor complex as a result of the active site serine being sulfonylated by the beta-sultam. Ring opening of the beta-sultam occurs by S-N fission in contrast to the C-N fission observed in the acylation of elastase by N-acylsulfonamides. Structure-activity effects are compared between sulfonylation of the enzyme and alkaline hydrolysis. Variation in 4-alkyl and N-substituted beta-sultams causes differences in the rates of inactivation by 4 orders of magnitude.     

Field fluctuation spectroscopy in a reverberant cavity with moving scatterers

We report a study of transient ultrasonic waves inside a reverberant cavity containing moving scatterers. We show that the elastic mean free path and the dynamics of the scatterers govern the evolution of the autocorrelation of acoustic wave field. A parallel is established between these results and a closely related technique, diffusing acoustic wave spectroscopy. Excellent agreement is found between experiment and theory for a moving stainless steel ball in a water tank, thereby elucidating the underlying physics, and a potential application, fish monitoring inside aquariums, is demonstrated.     

Spectroscopic study of neodymium-doped potassium-lead double chloride Nd3+:KPb2Cl5 crystals

Optical spectra, radiative and nonradiative transition intensities, and luminescence kinetics of neodymium-doped potassium-lead double chloride crystals Nd³⁺:KPb₂Cl₅, (Nd³⁺:KPC) are investigated. Crystals were grown by the Stockbarger-Bridgman technique. Experimental studies of absorption and luminescence spectra are performed, intensity parameters are obtained by the Judd-Ofelt method, radiative transition probabilities and branching ratios are calculated, and nonradiative transition probabilities are estimated. Luminescence kinetics of ² K _13/2, ² P _3/2, and ⁴ D _3/2 radiative levels of neodymium under selective excitation in the 355-nm region are studied.     

Tunable single sideband electro-optic ring modulator

A tunable single sideband electro-optic modulator has been devised which uses the principle of travelling wave resonance in a microwave ring circuit. Single sideband modulation is achieved by circularly polarising the microwave field; the design of the electro-optic cavity is discussed. This modulator is capable of shifting the frequency of a laser over a range of frequencies corresponding to the resonant frequencies of the microwave system and the feasibility of a practical device is considered.     

Trace metal assay of thorium oxide by atomic emission spectrometry

Summary An Atomic Emission Spectrometric (AES) method has been developed for the direct determination of twenty-two metallic elements at trace concentrations in thorium oxide. The method is based on the use of a d.c. arc — carrier distillation technique with 12% composition of a mixed carrier, viz. AgCl+SrF₂ in 5:1 proportion, and is equally applicable to both volatile and refractory analytes. A direct reading emission spectrometer with computerised data acquisition and processing facility has been used in these studies. The standardisation procedure includes study of volatilisation/excitation characteristics of the analyte elements to optimise choice and proportion of the carrier and signal integration time apart from optimisation of other experimental parameters such as arc current, viewing position of the arc plasma, sample charge etc. The detection limits for the analytes lie in the range 0.1–50 ppm while the precision of determinations is better than 15% for most of the elements as evaluated from the repetitive analyses of spiked samples.