Analysis of the Tautomeric Properties of 2-Formylcyclopentane-1,3-Dione Using the Data of IR Spectroscopy and Nonempirical (ab initio and DFT) Quantum-Chemical Calculations

The tautomerism, spectral properties, and properties of intramolecular hydrogen bonds in 2-formylcyclopentane-1,3-dione (FCPD) have been investigated by the methods of nonempirical quantum chemistry (calculations by the ab initio and DFT methods) and IR and ¹³C NMR spectroscopy. It is shown that FCPD in a crystalline form, as also does malonic dialdehyde, exists as self-associated enolized molecules with an open chelate ring. It is found that in solutions in CCl₄ the compound investigated exists as an equilibrium mixture of its exo- and endoenolic forms, with predominance of the former. The IR spectra of the solutions of FCPD in CCl₄ fix the presence of small amounts of the associate formed from the anionic and protonated forms of the substance. For the first time, the energies of the intramolecular H bonds of the endo- and exoenolic tautomeric forms in FCPD have been estimated theoretically. They appeared to be equal to 3.69 and 4.91 kcal·mole^–1, respectively. The possible mechanisms of enol-enolic interconversions of FCPD have been discussed.     

Manifestation of Intermolecular Interactions in the IR Spectra of 8-Azasteroids

We have investigated the intermolecular interactions of 8-aza-D-homogona-1,3,5(10),13-tetrane-12,17a-dione and 2,3-dimethoxy-8-azagone-1,3,5(10),13-tetran-12,17-dione with CHCl₃, binary solvents CHCl₃–CH₃OH, CCl₄–CHCl₃, and CCl₄–CH₃OH and also in the solid phase, which manifest themselves in the IR spectra. When the C=O groups of the studied 8-azasteroids form hydrogen bonding with the OH groups of alcohol, the frequencies (C=O) change insignificantly. We have found that they are higher than the corresponding frequencies in the IR absorption spectra of solid-phase samples, which is attributable not only to the effect of the medium but also to the possible shortened contacts of the C=O groups with the CH₃ and CH₂ groups of the molecules under study.     

Lifetimes of proton unstable states in 113I measured by the particle-X-ray coincidence technique

The -delayed proton decay of ¹¹³Xe was investigated by means of a total absorption -ray spectrometer and a telescope for particle detection. The energy window available for the -delayed proton decay of ¹¹³Xe and the relative branching ratios for proton transitions to the ¹¹²Te states were remeasured. The lifetimes of proton unstable ¹¹³I states populated in the electron capture decay of ¹¹³Xe were determined by means of the particle-X-ray coincidence technique. The results of the lifetime measurements are compared with statistical-model calculations.     

Precision measurement of the half-life and the decay branches of 62Ga

In an experiment performed at the Accelerator Laboratory of the University of Jyväskylä, the -decay half-life of ⁶²Ga has been studied with high precision using the IGISOL technique. A half-life of T_1/2 = 116.09(17) ms was measured. Using - coincidences, the intensity of the 954 keV transition and an upper limit of the -decay feeding of the 0⁺₂ state have been extracted. The present experimental results are compared to previous measurements and their impact on our understanding of the weak interaction is discussed.     

Specific Fluorescence Properties and Picosecond Transient Absorption of 8-Azasteroids

The specific fluorescence properties as well as picosecond transient absorption features have been studied for two 8-azasteroids. It is shown that at various excitation wavelengths the essentially different final excited electronic states are realized. Because of the multicenter character of 8-azasteroids the spectroscopic data obtained may be analyzed on a basis of the mesomeric tautomerism model taking into account the dynamic combination of cis- and trans-configurations. The dependence of fluorescence spectral characteristics on the solvent nature is a manifestation of intermolecular H-bond interactions.     

Amplification Coefficient of the Anti‐Stokes Component of Raman Scattering

The theory of intracavity parametric interaction of the components of Raman scattering is developed in the prescribedintensity approximation, which takes into account the reverse reaction of the excited waves to the pumpingwave phase. It is shown that one can substantially improve the conversion efficiency or the amplification coefficient of the antiStokes component by selection of the intracavity geometry, the optimum phase relation between the interacting waves, the pumping level, and the phase mismatch.     

Beta-decay studies of neutron-rich Sc- Cr nuclei

The neutron-rich nuclei ₂₁^{57, 58}Sc, ₂₂^58-60Ti, ₂₃^60-63V, ₂₄^62-66Cr have been produced at Ganil via interactions of a 61.8A MeV ⁷⁶Ge beam with a ⁵⁸Ni target. Beta-decay studies have been performed using combined - and -ray spectroscopy. Half-lives have been determined and -decay schemes are proposed for ⁵⁸Ti, ⁶¹V and ⁶²Cr. From these studies, new hints for the existence of -decaying isomers in ⁶⁰V and in ⁶²Mn are provided. These results are compared to shell model calculations. The role of the f_7/2- f_5/2 proton-neutron interaction is examined through its influence on the lifetime values.     

Linear Theory of the Beam-Wave Interaction in the Arbitrary Cylindrical Cerenkov Device

The hot dispersion equation in Cerenkov devices has been derived and analyzed numerically using the self-consistent linear theory. In principle, the linear analysis can be applied to efficiently calculating all kinds of beam-wave interaction in various Cerenkov devices composed of axisymmetric slow-wave structures (SWS) with arbitrary periodic profile. Then the results for Cerenkov devices with three typical SWS profiles are presented.     

Total absorption spectroscopy of the β-delayed proton emitter 117Ba

The very neutron-deficient ¹¹⁷Ba nuclei were produced in ⁵⁸Ni-induced reactions on a ⁶³Cu target and selected for spectroscopic studies by using BaF⁺ molecules formed in the ion source of the GSI on-line mass separator. The -decay of ¹¹⁷Ba was investigated by means of the total absorption -ray spectrometer and a telescope for -delayed particle detection. In the analysis combining the -delayed -ray and proton data the energy window available for -delayed proton emission, the branching ratios for proton transitions to the ¹¹⁶Xe levels and the -feeding of the -ray and proton-emitting ¹¹⁷Cs states were determined. The -strength function for ¹¹⁷Ba derived from the measured -feeding distribution revealed the existence of a broad resonance structure at ¹¹⁷Cs excitation energy of about 4-5 MeV. The results of the -delayed proton studies and -strength measurements are confronted with theoretical predictions.     

Analysis of the Tautomeric Properties of Substituted 3-Acryloyltetrahydrofuran-2,4-Dione According to the Data of IR Spectra and Ab Initio Quantum Chemical Calculations

The tautomerism and spectral properties of 3-[3-(4-methoxycarbonylphenyl-acryloyl]tetrahydrofuran-2,4-dione (MCPATD) have been investigated by the methods of nonempirical and semiempirical quantum chemistry (nonempirical calculations by the Möller–Plesset theory of 2nd-order perturbations, calculations by the AM1 and PM3 semiempirical methods), as well as by IR and ¹H NMR spectroscopy. It has been shown that the presence of an additional chain of conjugation in the side chain of MCPATD substantially changes its tautomeric composition and spectral properties as compared to 3-formyl- and 3-acetyltetrahydrofuran-2,4-diones. The frequencies and forms of normal vibrations calculated for each cis-enolic tautomer differ substantially within the region of vibrations of keto groups and double bonds, which makes it possible to identify the tautomers present in the mixture. It is found that in CHCl₃ solutions MCPATD exists as an equilibrium mixture of its exoenolic forms. The possible mechanisms underlying the enol-enolic conversions of MCPATD are discussed.     

Space Videophotometric System for Recording Optical Radiations in the Earth Atmosphere

This paper describes the VFS-3M videophotometric system designed for automatic remote recording of images and parameters of optical radiations following lightning discharges from aboard the Russian segment of the International space station. The characteristics of the system and the possibilities of recording such types of radiation as Red Sprites and Blue Jets are given.     

Synthesis of peptidomimetics using a polymer-bound Boc-linker

Boc-resin-bound -hydroxy--amino-aldehydes are accessible starting from N-terminally bound amino acidesters by using Dondoni's C₁-homologationreaction sequence. The conversion of these synthons totwo different peptide mimetics – 2-hydroxy-1,3-ethyl-diamines and -hydroxy--amino-vinyl sulfones – hasbeen investigated. The successful transfer of thecomplex -amino acid homologation reactionsequence into solid-phase chemistry demonstrates thepotentials of the Boc-resin for synthesis of peptidomimetics.     

The maximum entropy principle as a consequence of the principle of Laplace

The maximum entropy principle states that the probability distribution which best represents our information is the one which maximizes the entropy with the given evidence as constraints. We prove that this principle is implied from the Laplace principle of equiprobabilities applied to the setS of allN-term sequences of results which are compatible with the given evidence. We generalize to the information gain method of Kullback.     

Gravitational Waves in Matter

The theory of gravitational waves in matter is given. This covers the questions of constitutive relation, number of independent polarizations, index of refraction, reflection and refraction at an interface, etc. The theory parallels the familiar optics of electromagnetic waves in material media, but there are some striking differences. The use of the Campbell-Morgan formalism in which the gauge-invariant tidal force dyads E and B rather than the gauge-dependent metric perturbations are the unknowns is essential. The main justification of the theory at the moment is as a theoretical exercise worth doing. The assumption: size L of the medium gravitational wave length (infinite medium) rules out application to the already well-understood detection problem, but there may be an application to gravitational wave propagation through molecular gas clouds of galactic or inter-galactic size.     

On the initial layer solution of the Boltzmann equation with small Knudsen number

We extend our method of systematic removal of secular terms in a singular perturbation treatment of the Boltzmann equation with small Knudsen numbers to the initial layer. The requirement that the solution through the initial layer should connect smoothly to the normal solution removes an ambiguity noted in our previous paper. We show that removal of secular terms improves Grad's solution for the initial layer and reintroduces soundlike modes associated with higher moments, first found by Wang Chang and Uhlenbeck.     

Investigation of Rust Formed on Steel Surfaces and Related Oxyhydroxides

In order to indentity the corrosion products formed on steel surfaces from ⁵⁷Fe Mössbauer spectroscopy, detailed Mössbauer parameters have been determined for various kinds of iron-oxyhydroxides: -FeOOH, -FeOOH, -FeOOH and -FeOOH. ⁵⁷Fe Mössbauer measurements of the iron oxyhydroxides indicate the following results. Fe occupies a single site in -FeOOH, but below the Néel temperature as at e.g., 300 K the Mössbauer spectrum is always broad, showing a distribution of the strength of the magnetic exchange interactions. Its shape depends on the grain-size and synthetic methods of the specimen. Fe occupies 3 sites in -FeOOH. High-purity reagents of -FeOOH always contain small amounts of -FeOOH and their Néel temperatures depend on the synthetic methods of the specimen. Mössbauer spectroscopy of the synthetic -FeOOH shows very broad distribution of the hyperfine magnetic fields.     

Comment on the calculation of thermal averages by long-time Monte Carlo simulations

It is shown that the effect of turnovers of the whole spin lattice for temperatures below the ordering temperature during a long-time computer simulation is not always satisfactorily reduced by considering the absolute value of the order parameter. A simple method to overcome this problem is suggested.     

The Dependence of the Luminescence Intensity of Lanthanide Complexes with β-Diketones on the Ligand Form

The influence of -diketone forms on the luminescence intensity of lanthanide compounds in a series of ligands, acetylacetone (trifluoroacetylacetone, benzoylacetone)—their unsaturated analogues (monomeric form)—copolymers of the latter with styrene (methylmethacrylate), was studied. Lanthanides in compounds with copolymers have been established to demonstrate the brightest luminescence. It was found that its intensity depends not only on the character of the substituent (CH₃, CF₃, C₆H₅) in the -diketone molecule, but also on the distance between the -diketone fragments in the copolymer. Reasons explaining the high intensity of luminescence in lanthanide–copolymer compounds are considered.     

The Impact of the Phenyl Spacer on the Electronic Structure and Spectra of Porphyrin Dimers

Quantum-chemical investigation of the electronic structure and properties of the excited states of porphyrin dimers, in which monomeric subunits are linked by the phenyl spacer, is performed by semiempirical methods. The molecular orbitals of the monomeric subunits are shown to interact with each other via molecular orbitals of the phenyl ring. Comparison of the experimental absorption data and quantum-chemical calculations of electronic absorption spectra for different conformations of Zn-tetraphenylporphyrin dimer is performed and the main conformation of the dimer in a solution at 295 K, in which the planes of tetrapyrrole macrocycles are located at an angle of about 60°, is substantiated.     

Updated Analysis of Gallium Chelate and Vanadium Chelate Solutions with 4‐(2‐Pyridylazo)Resorcinol and Xylenol Orange

The characteristic factors of the gallium and vanadium chelates with the ligands 4(2pyridylazo)resorcinol (PAR) and xylenol orange (XO) have been determined with the aid of the principle of correction, which makes it possible to eliminate the influence of the surplus ligand in the solution of its chelate with methane (which makes calculation easier) and thereby provides a more acceptable method in comparison with others. The real molar coefficients of extinction of the chelates Ga and V with PAR and XO have been determined and a detailed calculation of the stoichiometric ratios of chelates has been made. The results have shown that the chelates formed have the following structure: Ga(PAR), Ga(XO), V(PAR)₂, and V(XO).