Quadratic Padé approximants and the intruder state problem of multireference perturbation methods

Simple and quadratic Padé resummation methods are applied to high‐order series from multireference many‐body perturbation theory (MR‐MBPT) calculations using various partitioning schemes (Møller–Plesset, Epstein–Nesbet, and forced degeneracy) to determine their efficacy in resumming slowly convergent or divergent series. The calculations are performed for the ground and low‐lying excited states of (i) CH₂, (ii) BeH₂ at three geometries, and (iii) Be, for which full configuration interaction (CI) calculations are available for comparison. The 49 perturbation series that are analyzed include those with oscillatory and monotonic divergence and convergence, including divergences that arise from either frontdoor or backdoor intruder states. Both the simple and quadratic Padé approximations are found to speed the convergence of slowly convergent or divergent series. However, the quadratic Padé method generally outperforms the simple Padé resummation. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

MECHANISM OF PHOTOREDUCTION OF THIAZINE DYES BY EDTA STUDIED BY FLASH PHOTOLYSIS-II. pH DEPENDENCE OF ELECTRON ABSTRACTION RATE CONSTANT OF THE DYES IN THEIR TRIPLET STATE

Abstract— The pH dependence of the apparent reactivity of thiazine dyes in their triplet states has been studied in aqueous solutions, using as electron donor HY^-3, the trianionic species of ethylene diamine tetraacetic acid (EDTA), in the pH range 4–8. The pH dependence is found to be related to a change in the degree of protonation of the triplet excited dye. The apparent reactivity and lifetime of two differently protonated forms of thionine, azur B and methylene blue were determined by classical and dye-laser flash techniques, making it possible to evaluate the rate constant for electron abstraction of these molecules in their triplet states. It is found that: (a) protonation on the ring nitrogen increases the electron-abstraction rate constant of the triplet-state species about twenty-fold, and (b) methylation on the side amino groups decreases it.     

PHOTOSENSITIZATION BY ANTIMALARIAL DRUGS

Abstract The antimalarial drugs, chloroquine, hydroxychloroquine, quinine, quinacrine, amodiaquine and primaquine and the local anaesthetic, dibucaine, were tested for in vitro photosensitizing capability by irradiation with 365 nm UV light in aqueous solutions. The ability of these compounds to photosensitize the oxidation of 2,5-dimethylfuran, histidine, tryptophan or xanthine, and to initiate the free radical polymerization of acrylamide was examined in the pH range 2-12. Chloroquine and hydroxychloroquine show maximal photooxidative behaviour when in the monocation form at pH 9, in contrast to quinine which is extremely efficient as the dication below pH 4. This pattern appears to relate to the fluorescence yield as a function of pH. Chloroquine in the monocation or neutral form was found to undergo dechlorination upon irradiation, and this correlates directly with its ability to initiate photo-polymerization of acrylamide. Quinine also gives rise to small polymerization rates, attributed to photo-ionization in the quinoline ring, yielding a cation radical. Amodiaquine, primaquine and quinacrine do not have significant photochemical activity in aqueous solution. Dibucaine exhibits a strong photosensitizing capability at low pH, similar to quinine.     

New synthetic route to diaminonitropyrazoles as precursors of energetic materials

Treatment of nitropyrimidine derivatives with (N-substituted) hydrazines (2 equiv.) gave 1-(substituted)-3,5-diamino-4-nitropyrazole, providing a very mild conversion of pyrimidines into pyrazoles. This reaction provided a convenient route to precursors for new efficient and insensitive explosives.     

Synthesis of time-optimal control of a second-order nonlinear process

The time-optimal control of a soft spring is discussed. The domain of controllability and the switching locus are described. It is shown that the switching locus changes in a discontinuous manner as the nonlinearity varies continuously.This research was partially supported by the Joint Services Electronics Program, Grant No. (4711) N00014-67-A-0226 ARPA 1129, and by NASA, Grant No. NGR 15-005-021.     

The57Fe magnetic hyperfine field in Au-Fe alloys (evidence favoring the two Fe-environment model of Au-Fe alloys)

Conclusions The results of our analysis strongly support our two Fe environment hypothesis. The critical concentration at about 12 at.% suggests that the dependence of H(0,x) on x undergoes a fundamental change at this concentration. Furthermore, the so-called critical concentration at about 17 at.% apparently has little to do with any fundamental alloy property. Rather, it reflects the 12 at.% critical composition when properties are analyzed in terms of the average rather than the local Fe concentration. The two Fe environments appear to have differing configurations.This work was performed under the auspices of the U.S. Department of Energy by the Lawrence Livermore National Laboratory under Contract No. W-7405-Eng-48.     

A Rapid Gas-Chromatography/Mass-Spectrometry Technique for Determining Odour Activity Values of Volatile Compounds in Plant Proteins: Soy,and Allergen-Free Pea and Brown Rice Protein

Plant-based protein sources have a characteristic aroma that limits their usage in various meat-alternative formulations. Despite being the most popular plant-based protein, the allergenicity of soy protein severely restricts the potential adoption of soy protein as an animal substitute. Thereby, allergen-free plant-protein sources need to be characterized. Herein, we demonstrate a rapid solid-phase-microextraction gas-chromatography/mass-spectrometry (SPME-GC/MS) technique for comparing the volatile aroma profile concentration of two different allergen-free plant-protein sources (brown rice and pea) and comparing them with soy protein. The extraction procedure consisted of making a 1:7 w/v aqueous plant protein slurry, and then absorbing the volatile compounds on an SPME fibre under agitation for 10 min at 40 °C, which was subsequently injected onto a GC column coupled to an MS system. Observed volatile concentrations were used in conjunction with odour threshold values to generate a Total Volatile Aroma Score for each protein sample. A total of 76 volatile compounds were identified. Aldehydes and furans were determined to be the most dominant volatiles present in the plant proteins. Both brown rice protein and pea protein contained 64% aldehydes and 18% furans, with minor contents of alcohols, ketones and other compounds. On the other hand, soy protein consisted of fewer aldehydes (46%), but a more significant proportion of furans (42%). However, in terms of total concentration, brown rice protein contained the highest intensity and number of volatile compounds. Based on the calculated odour activity values of the detected compounds, our study concludes that pea proteins could be used as a suitable alternative to soy proteins in applications for allergen-free vegan protein products without interfering with the taste or flavour of the product.     

Inhibition of corrosion of commercial mild steel in presence of tetrazole derivatives in acid medium

The inhibitive influence of tetrazole derivatives namely, 1-(9¹-acridinyl)-5-(4′-aminophenyl) tetrazole, 1-(9′-acridinyl)-5-(4′-hydroxy phenyl) tetrazole and 1-(9′-acridinyl)-5-(4′-chlorophenyl) tetrazole on the corrosion of commercial mild steel in 1 N hydrochloric acid medium was studied by weight loss method. The monolayer adsorption has been confirmed by fitting the data to the Langmuir adsorption isotherm. Weight loss studies have been carried out at 303K, 318K and 333K. Thermodynamic parameters like heat of adsorption, activation energy and free energy change have been calculated. The maximum inhibition of efficiency of tetrazole derivatives, 1-(9′-acridinyl)-5-(4′-amoinophenyl) tetrazole, 1-(9′acridinyl)-5-(4′-hydroxyphenyl) tetrazole and 1-(9′-acridinyl)-5-(4′-Chlorphenyl) tetrazole was found to be 60.59%, 89.00% and 92.74, respectively. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.