Fluorescence polarization of helical molecules cooled in a supersonic jet

The β-binaphthylene oxide molecules studied under supersonic cooling conditions have a number of specific properties due to their nonplanarity. Low-frequency vibrations of the molecules in the excited S1 state are higher than the frequencies for the S0 state, and conversely the high-frequency vibrations have lower frequencies. The S₀-S₂ fluorescence excitation spectrum is structureless. The absence of a Q branch in the rotational contour of the line for the purely electronic transition indicates that it is substantially broadened and shifted toward shorter wavelengths as a result of rotational perturbations of the helical structure of the molecule. Multiplet lines in the spectra of β-binaphthylene oxide complexes with argon, krypton, and xenon correspond to different isomeric complexes. Their bond energies are below those observed previously for planar polycyclic molecules such as perilene, fluorene, and carbazole. The greater number of isomers with xenon is due to strengthening of the bond in the van der Waals complex and the nonequivalence of the position of the xenon atoms on the outside and inside of the helical molecule. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 473–477, July–August, 2006.     

Comparative analysis of high-resolution spectra of naphthalene and its methyl-substituted derivatives cooled in a supersonic jet

We have carried out a comparative analysis of fine-structure fluorescence excitation and fluorescence spectra of naphthalene, 2,6-and 2,7-dimethylnaphthalene, and 2-methylnaphthalene molecules cooled in a supersonic jet. We have shown that both the frequencies and the intensities of most of the lines in the spectra of these molecules are correlated. Such a correlation facilitates interpretation of the spectra in the case when it is difficult to calculate the transition intensities and when lines corresponding to vibrations of different symmetry have close frequencies. For the considered molecules, a preliminary assignment of the lines in the fine-structure spectra is refined. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 336–340, May–June, 2007.     

Polarized Fluorescence of Jet‐Cooled Indole

The polarization of indole fluorescence on excitation in the P, Q, and R branches of a purely electron transition has been investigated. Relations are given to calculate the fluorescence polarization with arbitrary orientation of the dipole moments of transitions with absorption and emission and with excitation in the Q branch of the vibronic line. The coincidence of the measured (7.3%) and calculated (7.7%) values of the polarization degree confirms the reported intramolecular orientation of the dipole moment of transition. The measured fluorescence polarization degree on nonselective excitation is about 3%.     

Singlet-Singlet Electronic Excitation Energy Transfer in a Bichromophore Cooled in a Supersonic Jet

The fluorescence excitation spectra and polarization of the fluorescence of a bichromophore cooled in a supersonic jet are measured. The bichromophore consists of 2,5-diphenyloxazole (PPO) and 1-(5′-phenyl-1′, 3′-oxazole-2′-yl)-4-(5′-phenyl-1′,3′,4′-oxadiazole-2′-yl)-benzene (POPDP) connected by the methylene bridge -(CH₂)-. Based on the analysis of these components and theoretical calculations, it has been proven that the total intramolecular singlet-singlet transfer of the energy of electronic excitation from the energy donor PPO to the acceptor POPDP occurs in a time of 10⁻¹² sec. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 460–463, July–August, 2005.     

Spectral fluorescence and polarization characteristics of <Emphasis Type="Italic">Z,Z</Emphasis>-bilirubin IXα

We have studied the spectral fluorescence and polarization characteristics of Z,Z-bilirubin IXα, at room temperature in chloroform and in aqueous buffer medium, within an equilibrium complex with human serum albumin (HSA), and also under low temperature conditions (T = −100°C) in isobutyl alcohol. We have observed a bathochromic shift of the fluorescence spectra, which is most pronounced for the bilirubin-albumin complex. The following are considered as possible reasons for the observed dependence of the position of the fluorescence (fluorescence excitation) spectra on the excitation (detection) wavelength: structural and spectral differences between the chromophores making up the bilirubin molecule; conformational heterogeneity of the pigment in solution; a contribution to the fluorescence from molecules which have not completed the vibrational relaxation process; inhomogeneous orientational broadening of the levels; heterogeneity of the microenvironment of the chromophores in the protein matrix. We show that polarized fluorescence of bilirubin occurs at room temperature, due to the anomalously short fluorescence lifetime τ (picosecond or subpicosecond ranges). Despite such a short τ, the absorption and emission polarization spectra suggest the presence of intramolecular nonradiative singlet-singlet energy transfer when bilirubin is excited to high vibrational sublevels of the S₁ state (degree of polarization p = 0.11–0.12). When fluorescence is excited on the long-wavelength slope of the absorption band, no transfer occurs: the degree of polarization (p = 0.46−0.47) is close to the limiting value (p = 0.50). We discuss the question of the role played by exciton interactions between chromophores in the bilirubin molecule when it is excited. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 108–119, January–February, 2007.     

Fluorescence excitation spectra of jet-cooled carbazole complexes with monohydric alcohols

We have analyzed the fluorescence excitation spectra of carbazole complexes with a single molecule of methyl, deuterated methyl, ethyl, and propyl (1-propanol and 2-propanol) alcohols, cooled in a supersonic jet. We have determined the shifts in the fluorescence excitation spectra of the complexes relative to the frequency of the purely electronic transition of unbound carbazole. They occur as a result of formation of hydrogen bonds between the N-H group of the carbazole and the OH group of the alcohols. The frequencies of stretching vibrations of the hydrogen bonds with different alcohols vary within the range 150–157 cm⁻¹, while the frequencies of the bending vibrations vary in the range 21–22.9 cm⁻¹. From the shape of the rotational contours of the bands for the purely electronic and vibronic transitions of the complexes, we determined that they belonged to rotational conformers. We calculated the equilibrium configurations of the complexes in the ground state. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 756–760, November–December, 2007.     

Spectral characteristics of unstable flow in the mixing layer of supersonic underexpanded jet over its initial region

An experimental study of spectral characteristics of unstable flow in the mixing layer of supersonic axisymmetric underexpanded jets with Mach number M_a = 1 is reported. The destabilization of the flow is related to the formation, in the mixing layer of the jets, of disturbances in the form of streamwise vortical structures of the Taylor — Goertler type. As a result, in the mixing layer there forms an azimuthally non-uniform stationary distribution of total pressure. The Fourier transform of azimuthal sweeps of non-uniformity in pressure distributions was used to calculate the amplitude-wave spectra. An analysis of the spectral characteristics has allowed us to evaluate the longitudinal increment of amplitude growth of the disturbances and their dependence on the wavenumber and on the nozzle pressure ratio. The range of wavenumbers in which the streamwise vortical structures grow in amplitude is identified. This work was financially supported by the Russian Foundation for Basic Research (Grant No. 05-08-01215).     

Spectral and polarization properties of a composite material with filler of plant origin

Based on a filler of plant origin, we have developed a new composite material and have studied its spectral and polarization properties. We suggest a direction for application of the synthesized material. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 419–421, May–June, 2008.     

超声射流CCl2 自由基激光诱导荧光激发谱

用CCl4 /Ar混合气体脉冲直流高压放电产生CCl2 自由基 ,在超声射流冷却下获得了CCl2 A 1B1- X 1A14 40～ 5 80nm的K 结构分辨的激光诱导荧光激发谱 .通过K 结构分辨谱的分析 ,对 72 2条转动子谱带进行了归属 ,得到了激发态CCl2 A 1　B1的两个全对称振动模式的振动频率、非谐性常数和转动常数差值 ,即激发态的振动频率ω1=6 31.2 0cm-1,ω2 =30 2 .0 0cm-1,A′-B′ =3.476cm-1.     

Spectral characteristics of luminescence of solutions of complex molecules under conditions of electronic excitation transfer to a saturable acceptor in the case of inhomogeneous broadening of electronic energy levels

Spectral characteristics of solutions of complex molecules under conditions of inhomogeneous broadening of energy levels are considered in the case when the nonlinear dependence of the population of molecular states on the excitation intensity is determined not by saturation of molecular levels but by exchange of the electronic excitation energy with the environment. Calculations have shown that the dependence of the position of the fluorescence spectrum on the excitation frequency is nonmonotonic in solutions of the type and varies substantially with the excitation intensity. Belarusian State University, 4, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 2, pp. 164–168, March–April, 1997.     

Turbulence-induced changes in degree of polarization, degree of coherence and spectrum of partially coherent electromagnetic beams

Based on a recently formulated unified theory of coherence and polarization, a method is described to study turbulence-induced changes in the polarization, the coherence and the spectrum of partially coherent electromagnetic beams on propagation. The electromagnetic Gaussian Schell-model beam is taken as a typical example of partially coherent electromagnetic beams, and the closed-form expressions for the degree of polarization, the degree of coherence and the spectrum of electromagnetic Gaussian Schell-model beams propagating through atmospheric turbulence are derived in the quadratic approximation of Rytov's phase structure function. Some interesting results are obtained, which are illustrated by numerical examples and are explained in physics.     

Quasilinear fluorescence spectrum for anthracene in a gaseous phase with high resolution

Investigations performed on a DFS-454 high-resolution spectrograph with a dispersion of ～1 Å/mm are reported. The presence of a fine structure of the individual quasilines at T=418 K and p=0.29 torr is revealed. For a 390 cm^?1 vibration quasiline, six components that are grouped into doublets are recorded.     

Spectral-Luminescence Characteristics of Carbazole, Dibenzofuran, and Dinaphthofuran in the Gas Phase in Excitation by Electrons and Photons

The spectra of electron-energy loss, the excitation functions, and the fluorescence spectra in excitation of carbazole, dibenzofuran, and dinaphthofuran by monoenergetic beams of electrons of different energies are determined. The singlet-triplet transitions S ₀–T ₁ and the singlet-singlet transitions up to S ₀–S ₇ are recorded, which covers the region 2–11 eV. In the spectra of electron-energy loss, bands that refer to the n^ast and ^* transitions are identified. The replacement of the heteroatom of nitrogen by the atom of oxygen in the five-membered ring has no substantial effect on the spectra of electron-energy loss.     

大气湍流中部分相干光束上行和下行传输偏振特性的比较

以部分相干的电磁高斯-谢尔模型(electromagnetic Gaussian-Schell model, EGSM) 光束为研究对象, 根据相干和偏振的统一理论以及随机光束的Stokes参量, 推导出EGSM光束在大气湍流中斜程传输时的偏振度(degree of polarization, DoP)和偏振方向角的表达式, 研究了大气湍流中上行和下行传输时EGSM光束偏振特性的不同. 研究结果表明: 在相同条件下, EGSM 光束下行传输时整个光场DoP的分布比上行传输要集中; 下行传输时轴上点的DoP达到最大值所对应的传输距离长于上行传输. 可以看出, EGSM光束沿下行路径传输时, 探测器可以接收更远距离处的波束传输信息.     

Influence of conduction heat loss on enhancing the heat transfer performance of a square flat plate with constant heat flux by an impinging jet in cross-flows

An experimental setup was built to study the influence of conduction heat loss on the convective heat transfer performance enhanced by an impinging jet in cross-flows. Results revealed that the conduction heat loss ratio (E_c/E) is between 12.0% and 40.1%, and it decreases nonlinearly with the ratio of jet-to-cross-flow velocity. The relative Nusselt number increases with the ratio of jet-to-cross-flow velocity. The maximum peak value and the average are 8.1 and 6.4, respectively. The distribution of the relative Nusselt number seems to be flattened by assuming a constant conduction heat loss ratio.     

有源耦合腔激光器锁模特性研究

本文在理论上首次发现有源耦合腔激光器的自启动锁模和时域调制特性,并对其进行了全面的分析和计算.对有源耦合腔激光器的自启动锁模机制和时域调制特性给予详尽的数值计算结果和清晰的物理图象解释,提出在有源耦合腔锁模激光器中可用连续泵浦源代替锁模泵浦源,而且有产生更短的光脉冲可能性.     

Vibrational spectra of In2S3, CuIn5S8 and AgIn5S8 compounds with a spinel structure

The IR reflection spectra of In₂S₃, CuIn₅S₈, AgIn₅S₈ compounds with a spinel structure are investigated. Using the DA-K-K method, we determined the frequencies of longitudinal and transverse phonons, attenuation coefficients of phonons, and IR intensities, as well as the dielectric constants ε₀ and ε_∞. Belarusian State University of Information Science and Radioelectronics, 6, P. Brovka St., Minsk 220600, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 2, pp. 263–265, March–April, 1997.     

The order with respect to oxygen and the activation energy for the burning of an anthracitic char in O2 in a fluidised bed, as measured using a rapid analyser for CO and CO2

Measurements of the oxidation of a coal char in a fluidised bed have the advantages that the rates of heat and mass transfer to and from a reacting particle are large and characterised well. However, problems have arisen from a combination of the slow, but typical, response–time (4 s) of the analysers for CO and CO₂ and the slow mixing of gases when filling a fairly large fluidised bed. The resulting time constant for the sampling system was 8 s and comparable to the time for combustion at 900 °C or above. The purpose of this work was to measure the kinetics of oxidation of a char in a smaller fluidised bed (with a shorter mixing time) using an analyser for CO and CO₂ with a response time as low as 0.1 s. The result is that the oxidation of an anthracitic char is now found to be first order in O₂ between 700 and 900 °C; at 900 °C the order previously measured was almost zero. The activation energy is now measured here to be 145 ± 25 kJ/mol, in agreement with some early work.