Calculation of the Tautomeric Properties of 3‐Formyl‐Tetrinic Acid by the ab initio and DFT Methods

We have carried out a nonempirical quantumchemical calculation with full optimization of the geometry of all theoretically possible tautomeric forms of 3formyltetrinic acid (FTRA) according to the Møller–Plesset secondorder perturbation theory with the use of a 6–31G(d) double zeta basis set. The correlation corrections to the total energy of molecules for optimized geometric configurations were calculated in the 631G(d,p) basis. All the possible tautomeric forms of FTRA and the harmonic vibrational frequencies were also calculated within the density functional theory (DFT) with the use of the Perdew–Burke–Ernzerhof (PBE) functional in a threeexponent basis. It is shown that FTRA in vapors (in the perfect gas approximation) exists in the form of a mixture of three enol forms, among which two exoforms predominate. The frequencies and forms of normal vibrations for each cisenol tautomer in the region of vibrations of ketogroups and double bonds differ widely, which permits identification of the tautomers present in the mixture. The possible mechanisms of enolenol transformations of 3acyltetrinic acids are discussed.     

Calculation of Out‐of‐Plane Vibrations of a Porphin Molecule

Using the DFT/B3LYP method with the base set 631G^**, we carried out calculation of the frequencies of the normal vibrations of porphin and of its five isotopic types. Scaling of force constants for outofplane vibrations has been performed in independent natural coordinates. The symmetry coordinates are introduced and a force field for outof plane vibrations of a porphin molecule in independent coordinates of symmetry is obtained. A new correlation of the frequencies of vibrations in the type of the symmetry B _1u for the isotopic type of the d ₂ porphin molecule is suggested on the basis of discrete analysis of the distribution of a potential energy.     

Equations for the Magnetization Modes in a System Having a Quadruple Nucleus with the Spin S = 1

Within the framework of the method of a density matrix, differential equations are obtained that describe the evolution of the modes of magnetization <Î₊>, <Î_{+ z} >, and <Î_{+ z} ²> for a spin system containing a nucleus with a 1/2 spin connected scalarly with the quadruple nucleus of the spin S = 1 in the presence of crosscorrelation between the dipole ISinteractions, anisotropy of the chemical shift of the I and S nuclei, and quadruple interaction of the S nucleus. The equations are used for analysis of the evolution of the intensities of each line in the triplet of the Raman spectrum of the 1/2 spin. Expressions for the times of crossrelaxation and the times of transverse relaxation of each of the lines of the triplet are obtained.     

Manifestation of Extracoordination in the Resonance Raman Spectra of Water‐Soluble Cation Co‐Porphyrins

Resonance Raman spectra (RRS) of Co(II) and Co(III)5,10,15,20tetrakis(4Nmethylpyridinium)porphyrin ((Co^II(TmpyP4), and Co^III(TMPyP4)) in aqueous solutions at different pH as well as in organic solvents (methanol, ethanol, DMSO, DMF) are obtained. The increased sensitivity of the oscillation frequencies ₂, ₄, ₈, and ₆ — the markers of the oxidation state of a metal — to the nature of an axial ligand has been revealed. For Co^III(TmpyP4), the shifts of the indicated frequencies in extracoordination have turned out to be twofold larger than those for Co^II(TmpyP4). The spectral effects observed are related to different electron influence of the extraligands on the system of the porphyrin ring. In the case of Co(III)porphyrin, interaction of the d orbitals of the metal and the e _g ^*orbitals of the macrocycle is more efficient since its ionic radius is smaller than for the Co(II)complex. For Co^III(TmpyP4), a linear correlation between the oscillation frequencies ₂, ₄, ₈, and ₆ and the experimental Gutmann parameters characterizing the electronacceptor properties of solvents is found.     

Infrared Spectroscopic Study of N,N‐Dimethylthioformamide Complexes of the Hofmann Type

Four new Hofmanntype complexes, M(DMTF)₂Ni(CN)₄, (where DMTF is dimethylthioformamide, M=Mn, Cd, Co, or Ni) were synthesized and their structure was determined by an elemental analysis and infrared spectroscopy. The IR spectra of DMTF and its nickel tetracyanine complexes with Mn(II), Cd(II), Co(II), and Ni(II) have been investigated within the range 4000–400 cm^–1. The frequency shifts in the metal complexes agree with the assignment of the CS and CN frequencies. The complexes consist of infinite planar polymer layers of |MNi(CN)₄|. Ndimethylthioformamide is coordinated to this layer from above and below; it is a monodentate ligand and is Sbonded through the metal atom in these complexes.     

A Cathodoluminescent Screen of Columnar Structure for Field Emission Displays

We have suggested and implemented a method of creation (growing) of sublimatescreens formed by singlecrystal luminophor columns which are perpendicular to an amorphous (e.g., glass) substrate. The diameters of the columns are 3–5 m, the height 7–10 m. The columnar singlecrystal structure of the screen ensures the high light yield and radiation color needed for field emission displays. It is possible to select the growing regime so that the columns are very closely spaced (1–2 m). The gaps can be filled with a conducting opaque material that increases the contrast of the screen and improves their electrical conductivity.     

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).     

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.     

Absorption Spectra of Pentamers of Tetrapyrrole Compounds in Aqueous Solutions

Pentamers of two types have been obtained in aqueous solutions containing mixtures of two tetrapyrrole compounds, in whose molecules there are positively or negatively charged peripheral groups. The pentamers of one type include one molecule of mesotetra(4Nmethylpyridyl) porphin (TMPP) and four molecules of the complex of mesomono(nsulfophenyl)etioporphyrin II with palladium (PdSPhEP), and the pentamers of the other type include one molecule of sulfonated phthalocyanine (PCS) and four molecules of TMPP. The absorption bands of the pentamers are broadened and shifted toward longer wavelengths in comparison with the bands obtained as a result of the addition of the spectra of the monomers. It seems that the changes in the absorption spectra are first of all due to the change in the interaction of the molecules of the pigments with the molecules of the surrounding in formation of associates and due to the influence of the resonance dipoledipole interaction between the molecules in the associates. The influence of the intermolecular photoinduced charge transfer is also possible (it is most probable for the associates with PCS). We have revealed an effective quenching of the fluorescence of PCS and TMPP solutions upon heteroassociation.     

Microwave Photonic Signal Down‐Conversion Using a Novel Two‐Frequency Bragg Grating Based Brillouin Fiber Laser

A simple technique using a novel twofrequency Bragg grating based Brillouin fiber laser to downconvert high frequency microwave photonic signals is presented. The mechanism of the Brillouin fiber laser and the principle of this technique for microwave photonic signal downconversion are analyzed. The 12GHz microwave photonic signals are experimentally downconverted to 1.13GHz IF signal with the technique.     

Anti‐Stokes Luminescence of Cadmium Telluride Nanocrystals

For the first time, the antiStokes luminescence in colloidal solutions of CdTe nanocrystals on excitation below the absorption edge has been discovered. The maximum spectral shift to the shortwave region relative to the excitation energy E _con ^max = 319 meV is obtained for meansized nanocrystals (2.5 nm). The conversion efficiency of the absorbed radiant energy is 1.3·10^–2%. The rise in the antiStokes photoluminescence intensity with increasing temperature and the linear dependence on the exciting radiation intensity have been established. It is shown that the effect observed cannot be caused by twophoton excitation or by Auger recombination. It is assumed that the basic mechanism of the luminescence observed is the radiative recombination through the energy levels of the states attributable to the disturbance of the crystal structure in the nanocrystals.     

Influence of Thermal Annealing and Deposition Conditions on the Structure and Optical Properties of GRS‐Active Substrates Based on Silver Films

Using the methods of atomicforce microscopy, xray diffractometry, and spectrophotometry, we have studied the morphological, structural, and optical characteristics of GRSactive substrates based on original and annealed silver films. We show that the backing temperature during deposition is the factor which exerts the most substantial effect on the morphological and optical properties of silver films and also on their stability with time. The coefficients of the correlation of the deposition rate with the characteristics of the optical density spectra of silver films are calculated. It is found that hightemperature (350°C) annealing of a silver film leads to the selforganization of its surface into a quasiperiodic structure with semiellipsoidal islets. The contribution of the processes of excitation of plasma resonances to the formation of the optical density spectra is discussed. It is shown that as a result of thermal modification the concentration of the crystalline phase of silver in a silver film increases 2–3 times and also the dispersion of the orientation of crystallites decreases.     

Information Potentialities of the Optical‐Capacitance Spectroscopy of Semiconductors

The opticalcapacitance spectroscopy method and the means for its implementation are described. The results of experimental investigations of semiconductors are compared with the known data obtained by other methods. The information potentialities and advantages of the opticalcapacitance spectroscopy are shown.     

Influence of Close‐Range Dipole‐Dipole Interactions on the Real Part of the Susceptibility of a Dense Resonance Medium

Based on a solution of the stationary modified Bloch equations, an investigation is made of the influence of the effect of internal optical bistability (IOB) on the behavior of the refractive index of a dense resonance medium as a function of the constant b of closerange dipoledipole interactions, frequency detuning, and the intensity of optical radiation. The conditions of existence of the IOB effect of the system dense resonance medium + optical radiation are found and the dynamics of the loop width of the hysteresis dependence of the population difference of the resonance levels of the medium on the characteristics of the system is traced. The domains of the parameters are determined in which the effects of selffocusing and selfdefocusing of the radiation propagating in a dense resonance medium can take place.     

Procedure for Automated Measurement and Calculation of the Electrophysical Parameters of Solar Cells

We described the procedures for automated measurement and calculation of the electrophysical parameters of solar cells on the basis of the IBM PC, a solar radiation simulator, V721A digital voltmeters, and a programcontrolled potentiometer which ensure the programmed assignment of the load resistance in the range 0.002–15,000 and measurement of the light voltampere characteristics of the solar cells, a shortcircuit current, and the opencircuit voltage and also calculated the basic parameters of the solar cells, such as the efficiency, the fullfactor of the voltampere characteristics, optimum and maximum power, optimum load resistance, series and shunt resistance, and the matching factor for the ideal and experimental voltampere characteristic of the solar cells. The error in the measurement and calculation of the solar cell parameters does not exceed 0.2%.     

FIR Photonic Microwave Filter Design Employing Simulated Annealing Algorithm

Photonic microwave filters are important parts of fiberoptic microwave/millimeter wave processing systems. In this paper, the synthesis problem of fiberoptic FIR microwave filters is addressed and a novel method for designing photonic microwave filter employing a simulated annealing (SA) algorithm is proposed. The design problem of photonic microwave filter can be reduced to be a multivariable function optimization problem, which can be solved by a simulated annealingbased algorithm. As an illustration of the application of SA to photonic microwave filter design, the synthesis of an optimizedFBGbased photonic microwave filter is discussed. Numerical results show that the global minimum finding capability of SA makes it be an efficient way to design the photonic microwave filter. Numerical results also demonstrate that the proposed method can be applied to design different filtering systems with different constraints.     

Triplet‐Triplet Electron Excitation Energy Transfer in the Gas Phase for the Carbazol–Diacetyl Donor‐Acceptor Pair

For the carbazol–diacetyl donoracceptor pair, the features of exothermal triplettriplet (TT) transfer of electron excitation energy in the gas phase upon excitation of carbazol by the nitrogen laser radiation which is not absorbed by diacetyl have been investigated. The luminescence spectra of carbazol in the gas phase have been studied. It is shown that carbazol phosphorescence in the gas phase is absent. Therefore, for estimating the TT transfer efficiency and its temperature dependence, in the kinetic approximation the dependences of the intensity of timeresolved delayed fluorescence of carbazol and sensitized phosphorescence of diacetyl on diacetyl pressure have been analyzed. It has been found that in the gas phase the features of the electronic structure of the molecules under investigation are responsible for the low efficiency of transfer (2·10^–4 at 453 K), which increases by an order of magnitude with increasing temperature in the 453–513 K range despite the increasing influence of the back transfer.     

Spectral‐Luminescence and Generation Properties of 1‐Aza‐2‐Methyl‐6‐Aminopyrene and of Its Protolytic Forms

Spectral manifestations of protolytic forms of 1aza2methyl6aminopyrene in ethanol and aqueous solutions are investigated. The ionization constants of the protolytic forms are determined. The generation properties and photostability of a neutral molecule and a cation in excitation by an excimer XeCl laser are studied.     

An ARC Facility for Studying Carbon Plasma and Obtaining Low‐Dimensional Carbon Structures

An experimental DUF2000 facility for spectroscopic investigations of a reducedpressure carbon arc and also for production of lowdimensional carbon structures (fullerenes, nanotubes, etc.) is described.     

Possibility of Using the Effect of Radio‐Optical Resonance for Spectral Analysis of Radio Signals

The absorption spectrum of optically oriented Cs atoms which is induced by a train of radiofrequency pulses is compared to the spectral components of the radio field. Possibilities of using the results obtained in the development of widerange microwave spectrum analyzers of high resolution are indicated.