Influence of Solvent Polarity and Viscosity on Nonradiative Processes in Oligothiophenes with Intramolecular Charge Transfer

By the methods of luminescence, picosecond spectroscopy, and quantumchemical calculations the mechanisms of electron excitation energy deactivation in some oligothiophenes with intramolecular charge transfer depending on the solvent polarity and viscosity have been investigated. While for 2Npiperidino5(2,2dicyanovinyl)thiophene (PDCVT) the main channel of nonradiative deactivation is the transition to a lower intermediate state with a twisted double bond controlled by the medium viscosity, in the case of (E){2[25piperidino2thienyl]6(trifluoridemethyl)4H4pyranylidene}propanedinitryl (PTFDN) fluorescence quenching is initiated by the solvent polarity. For two other oligothiophenes, 2Npiperidino5cyanothiophene (PCT) and 2Npiperidino5cyanoterthiophene (PCTT), differing in the length of the thiophene chain, we have revealed, along with the effective quenching of fluorescence in shortchain PCT (independent of the solvent polarity and viscosity), an increase in the radiation capacity in PCTT with increasing polarity of the solvent. The possible mechanisms of nonradiative deactivation in the investigated oligothiophenes are discussed.     

Monochromatization of synchrotron radiation for nuclear resonant scattering experiments

An introduction to monochromatization of synchrotron radiation in the energy range of 5–30 keV is presented for applications involving nuclear resonant scattering. The relevant relationships of the dynamical theory of Xray diffraction are used to explain basic concepts of monochromatization. These relations are combined with raytracing techniques to design highenergyresolution monochromators. Transmissionoptimized and energyresolutionoptimized designs that achieve high energy resolutions (10⁶)< E/E < 10⁸) are discussed separately. Practical silicon monochromators of both types are presented for a variety of nuclear resonances in this energy range.     

Absorption Spectra of Excited Ruby Crystals

We have investigated the absorption spectra of excited laser single crystals of ruby. The longlived increase in absorption depending on the degree of excitation is observed in optically excited crystals of ruby in a wide spectral range. Moreover, in the absorption spectrum of a postexcited ruby we discovered the excitationinduced longlived kinetic instability, namely, the noiselike quasiline component variable in time and over the spectrum and imposed on the smooth spectral curve.     

On the Effect of Increasing the Radiative-Transition Rate Near a Nanosize Point

A short review of theoretical and experimental studies concerning the photoexcited florescence and Raman scattering of light for a substance in a space containing small material bodies is presented. Calculations of the radiativetransition probability for atoms (molecules) in the vicinity of bodies with a size much smaller than the light wavelength are performed. The probabilities of the singlephoton and doublephoton transitions are shown to increase by factors of 9 and 81 in the vicinity of a nanosize sphere with dielectric constant ||\ 1. The probability of a radiative transition in the vicinity of the vertex of a conic needle bearing up against a plane (both with || 1) increases by factors of (/R _in)² and (/R _in)⁴ for singlephoton and doublephoton transitions, respectively (R _in is the curvature radius for the needle vertex). This theoretical result is suggested as an explanation of the effect of increasing the radiation process intensity in the experiments carried out in the studies cited below.     

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.     

Segregation of Components as a Result of High‐Power Laser Irradiation of Heterogeneous Condensed Media

The effects of periodic segregation of components in metastable (supercooled or supersaturated) binary alloys in the course of kinetic phase transformations as a result of laser irradiation of heterogeneous systems were studied analytically. Nonlinear processes of temporal and spatial selforganization of concentrationrelated structures were simulated using (i) a selfconsistent system of timedependent twodimensional equations for the distribution function for the sizes and spatial coordinates of the newphase particles and (ii) balance equations for the temperature and concentration of dissolved components; the latter equations account for nonlinearity of the particlesource function, sinks, for dependences of the phasetransition temperature on the surface curvature of particles and on the concentration of components, and for diffusive motion of particles in space. The domain of existence for the instabilities under consideration and the characteristics of the formed crystallizationrelated periodic structures are determined. It is established that nanoclusters formed during supersaturation of crystallizing material may play an important role in generation of selfoscillatory crystallization modes. Hydrodynamic aspects of liquidphase concentrationrelated stratification in heterogeneous systems based on immiscible components are considered.     

Spectral Complex for Controlling the Parameters of the Plasmachemical‐Reactor Working Medium

An automated spectral complex for controlling the parameters of the plasmachemicalreactor working medium by the emission and absorption spectra in the 200–1100 and 2000–5000nm ranges has been developed. To record radiation, a CCD array and a pyroelectric detector are used. Control of the spectral device functions, data recording, and the obtaining of results reflecting the workingmedium parameters and the concentration in it of components being measured are carried out by means of a personal computer. The complex makes it possible to study the temporal behavior of the workingmedium parameters being measured with a resolution of up to 10^–2 sec.     

Modeling and Simulation of Saturation Gain of IR Integrated Photonic Amplifiers

IR integrated photonic amplifiers at 1.55m operation will have good foreground in optical phasedarray radars for splitters and signal processing. The saturation gain characteristics of IR integrated photonic waveguide amplifiers (taken Er³⁺Yb³⁺ co-doped phosphate glass waveguide amplifiers as an example) are studied theoretically. For the homemade laser glass materials the calculated saturation intensities are 2.22kw /cm² for signal and 10.15kw/cm² for pump. The effects of absorption saturation of signal and pump lights on the gain of amplifiers 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.     

Stability of an SHF Discharge Running in a Resonator‐Type Plasmatron on the Basis of a Waveguide‐Slit Applicator

Using the method of optical emission spectroscopy, the dynamics of the development and extinction of a pulsating SHF discharge, its time instability, and the ranges of stable pressurerelated operation of a resonatortype SHF plasmatron on the basis of an annular waveguideslit applicator were investigated. It is found that at the pressures of CF₄ and its mixtures with oxygen optimal for breakdown a virtually complete lack of reproducibility of the signals of the components of the emission spectrum (in particular, of the FI 703.7nm line) from pulse to pulse of the discharge has been established. A discharge in oxygen in the investigated range of pressures and powers is characterized by a good repetition of the form of the pulses of the emission spectrum line (considered in relation to the OI 844.6nm line).     

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.     

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.     

Heterogeneous Chemiluminescence of Crystal Phosphors on X‐Ray or UV Irradiation

Using a highvacuum assembly with molecular beams and setups with an implemented atom probe, we investigated atomic and molecular adsorption luminescence of the oxides CaOBi and MgO in O and O₂ beams and also radicalrecombination luminescence excited by H and O atoms in ZnS and in ZnS,CdS samples activated with silver, copper, and the rareearth element Tm. It is established that exposure to UV light and xray radiation of the CaOBi, MgO, and ZnSTm samples, where the mechanism of direct excitation of heterogeneous chemiluminescence (HCL) is realized, does not influence the characteristics of the heterogeneous chemiluminescence, whereas similar exposure of the ZnS,CdSCu,Al and ZnS,CdSAg samples and of selfactivated ZnS, in which the excitation of heterogeneous chemiluminescence is due to the ionization of the lattice, leads to an increase in the intensity of heterogeneous chemiluminescence up to five orders of magnitude. The mechanisms of the phenomenon are considered.     

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.     

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%.     

Calculation of Quantum‐Chemical Characteristics of the Ground and Excited Electronic States of Porphin and Its Tetrapyrrole Isomers

Using the CNDO/S method, we have performed quantumchemical calculations of the ground and excited electronic states of porphin molecules (symmetry D _2h ) and a number of porphin isomers: porphycene (C_2h ), hemiporphycene, corphycene (C_2v ), isoporphycene, and three nonsynthesized structural isomers of the porphin skeleton by its bridge groups —(CH) _meso —. The results of the calculations are compared with the corresponding data for the freebase porphin molecule (H₂P). Near the boundary between the occupied and vacant orbitals the isomers form rows of singleelectron levels with similar energy characteristics. For the MOs of these isomers, the H₂P MOs closest in distribution on the comparable atomic centers are given. The weak (Q) and strong (B) transitions in the visible and near UV regions point to the porphyrin type of spectra of all the isomers. The calculation data on the excited electronic states of N, g, and ntype H₂P near and above the B states are given; the presence of such states in other isomers is shown. The calculation does not point to a difference in the position of the first singlet transitions in the first five isomers. The calculation data on the lower singlettriplet transitions are also reported.     

Two‐Wave CO2 Laser with Loss Modulation in Both Channels

The nonlinear dynamics of a twowave CO₂ laser with continuous pumping by an electric discharge and loss modulation in both channels is investigated theoretically. In modulation of losses with the same frequencies it is possible, by changing the shift of the phases of modulating signals, to monitor simply enough the amplitude, form, duration, and depth of modulation and also the repetition rate of radiation. Depending on the shift of phases, the maximum response can be concentrated in the lowfrequency region or propagate also to the region of high frequencies. If losses in both channels are modulated with different frequencies, a change in the relationship between these frequencies predominantly leads to a change in the shape, magnitude, and structure of response in the lowfrequency region of the amplitudefrequency characteristic (AFCh). In the highfrequency region of the amplitudefrequency characteristic, beginning from the peaks of the doubling of the vibration period, where inphase modes of radiation are implemented, the response virtually does not change. Similar regularities are observed on change in the shift of phases.     

Beam Optics and Signal Analysis in a Quantumlike Approach

The application of the tomographic map introduced recently in quantum mechanics is discussed in connection with classical problems that are described by equations formally coinciding with the equations of quantum theory. Examples of the classical problems such as chargedparticlebeam transport and analyticsignal analysis are reviewed. Some aspects of possible applications in quantum computing and quantum communication are discussed.     

Spectral Analysis of a Hardening Medium Based on I‐20A Oil

Chemical conversions occurring in a hardening medium based on I20A mineral oil through its servicelife are investigated by spectroscopy methods in the IR, visible, and UV regions and by luminescence, massspectroscopy, and elemental analysis methods. The possible reasons leading to deterioration of its cooling properties are established. IR spectroscopic techniques of quantitative determination of the content of compounds in a hardening medium that negatively and positively influence its cooling ability are suggested.     

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.