Lability of the Configuration of Free Complex Molecules and Polarized Luminescence

We compare the sensitivity of the degree of polarization of integral fluorescence for excitation by light with a spectral width larger than the width of the rotating loop or only in the Qbranch of the rotating loop to a change in the principal moment of inertia (rotational constants) of complex molecules in vapors. It is shown that the sensitivity depends on the degree of asymmetry of the molecular top and the intramolecular orientation of the dipole transition moments. Improvement of the symmetry of the asymmetric top leads to an increase in the sensitivity to at least one of the rotational constants. Such effects are also noted for the sensitivity of the period of the rotational quantum echo to a change in the rotational constants.     

Circularly Polarized Luminescence of Free Complex Molecules in a Constant Magnetic Field

It is shown that the magnetic fieldinduced optical activity in the luminescence of complex molecules in vapors in the presence of rotational anisotropy in the ensemble of luminescent molecules provides information also on the intramolecular orientation of the initiating dipole moments of transitions, including borrowed ones. The relationships between the rotational force of the optical activity and this orientation in the case of anisotropy induced by a linearly polarized exciting light are obtained.     

Polarization Kinetics of the Fluorescence of Solutions of Complex Molecules Undergoing Impulse Optical Quenching

The influence of optical quenching on the polarization of the integral (in time) fluorescence of solutions of complex molecules using picosecond pulses has been investigated theoretically. The resulting dependences of the degree of polarization on the time shift of pulses for the case of a thin layer of a medium (with no regard for the change in the intensity of the pulses) are in qualitative agreement with the results obtained for quasistationary excitation. A calculation has been made for the case of an extended medium with regard for the amplification of the quenching pulse. It is shown that scanning of the degree of polarization along the length of the cuvette makes it possible to obtain additional information on the mechanism of optical quenching in solutions and on the routes of deactivation of the energy of the molecule's excited state.     

Polarization States of Light and Their Quantum Tomography

The notion and main features of polarization states of light are discussed within the framework of classical and quantum optics. This notion is shown to be correctly defined for arbitrary light beams only within quantum optics by using the P-quasispin formalism developed earlier. Polarization states of quantum light are shown to be fully described by a polarization density operator (PDO) obtained via reducing the total field density operator. Theoretical foundations are given for quantum tomography of polarization states of light fields considered as a way of measuring PDO. Herewith, the main attention is paid to a method where proper polarization tomographic observables (PDO “measurers”) are used. The method is shown to be adequately formulated by means of quasi-spectral tomographic expansions of PDO in special operator bases (given by finite sums of partially orthogonal projectors), which determine probability distributions of tomographic observables as expansion coefficients. Matrix versions of such “tomographic” PDO representations are obtained. In particular, projections of these expansions on quasiclassical operator bases, determining polarization quasiprobability functions, are given. An example of experimental implementation of polarization tomography of unpolarized light (biphoton radiation with hidden polarization) is analyzed.     

Effect of Supercollisions on Energy Transfer in Mixtures of Bath Gases and Laser Excited Complex Molecules

Intensities and decay rates of delayed luminescence (DL) initiated by a pulse of N₂ laser were employed to probe collisional relaxation of complex molecules (benzophenone, acetophenone) diluted with bath gases Ar, Kr, Xe, C₂H₄, SF₆, C₅H₁₂. It was shown that vibrational relaxation can be interpreted in terms of two consecutive processes: vibration-vibration (V-V) and vibration-translation (V-T). The results clearly demonstrated that fast component of DL can be used to study V-V energy transfer. It was found that at relatively small internal energy the collisional efficiences of V-V process had the values typical for molecular processes in which supercollisions contribute. The average energies transferred per collision, (ΔE), well correlated with predictions of the simple ergodic collision theory of intermolecular energy transfer.     

Stress-Induced Alteration of Chlorophyll Fluorescence Polarization and Spectrum in Leaves of <Emphasis Type="Italic">Alocasia macrorrhiza</Emphasis> L. Schott

The value of intrinsic chlorophyll fluorescence polarization, and the intensity in emission spectrum were investigated in leaf segments of Alocasia macrorrhiza under several stress conditions including different temperatures (25–50°C), various concentrations of NaCl (0–250 mM), methyl viologen (MV, 0–25 μM), SDS (0–1.0%) and NaHSO₃ (0–80 μM). Fluorescence emission spectrum of leaves at wavelength regions of 500–800 nm was monitored by excitation at 436 nm. The value of fluorescence polarization (P value), as result of energy transfer and mutual orientation between chlorophyll molecules, was determined by excitation at 436 nm and emission at 685 nm. The results showed that elevated temperature and concentrations of salt (NaCl), photooxidant (MV), surfactant (SDS) and simulated SO₂ (NaHSO₃) treatments all induced a reduction of fluorescence polarization to various degrees. However, alteration of the fluorescence spectrum and emission intensity of F₆₈₅ and F₇₃₁ depended on the individual treatment. Increase in temperature and concentration of NaHSO₃ enhanced fluorescence intensity mainly at F₆₈₅, while an increase in MV concentration led to a decrease at both F₆₈₅ and F₇₃₁. On the contrary, NaCl and SDS did not cause remarkable change in fluorescence spectrum. Among different treatments, the negative correlation between polarization and fluorescence intensity was found with NaHSO₃ treatments only. We concluded that P value being measured with intrinsic chlorophyll fluorescence as probe in leaves is a susceptible indicator responding to changes in environmental conditions. The alteration of P value and fluorescence intensity might not always be shown a functional relation pattern. The possible reasons of differed response to various treatments were discussed.     

不同调制方式下偏振度与偏振模色散的关系

给出了偏振度与偏振模色散关系的理论模型,分析了非归零和归零两种调制方式下的偏振度与偏振模色散关系特性,结果表明偏振度町以作为实时检测偏振模色散的信号;且偏振度对偏振模色散的有效检测范围不大于调制光信号的占空比α,同时检测灵敏度与有效检测范围成反比;在非归零调制时偏振度对偏振模色散的有效检测范围最宽,为调制光信号的一个调制周期,是常规归零调制(占空比为0．5)时的2倍,但灵敏度只有常规归零调制时的一半。进一步探讨了在实际应用中改善偏振度对偏振模色散的有效检测范围和灵敏度的方法。实验验证了非归零调制时偏振度与偏振模色散关系特性。     

Effect of the reabsorption or radiation in the lines on the rate of ionization and recombination processes in a nonequilibrium plasma

To whom correspondence should be addressd.     

Twin boundaries with 9R zone in Cu and Ag studied by quantitative HRTEM

When highly inclined against the {111} plane of the coherent twin boundary, 3 110 tilt boundaries in Cu or Ag have a complex structure. As the boundary plane approaches the symmetrical {211} orientation, the grain boundaries decompose into two phase boundaries. Between these phase boundaries the metal adopts a rhombohedral crystal structure, denoted as 9R. Not the {211}-oriented boundary, but a boundary inclined by 8° against {211} has the minimum energy in this family of grain boundaries with 9R zone. Using high resolution transmission electron microscopy, we have studied the atomistic structure of this special boundary. An iterative structure refinement based on quantitative image analysis reveals the atomistic structure of the grain boundary at a well-defined level of confidence. Comparing the refined grain boundary structure with a model obtained by molecular statics calculations exposes small, but significant discrepancies. These probably arise because in the model the stacking fault energy is too small and the short distance repulsion is too weak. Grain boundaries of equivalent geometry in Ag and Al exhibit different widths of the 9R zone. Experimental observations support a theory relating the equilibrium width of the 9R slab to the stacking fault energy and the elastic properties of the material.Presented at the Workshop on High-Voltage and High Resolution Electron Microscopy, February 21–24, 1994, Stuttgart, Germany.     

Calculation of crosstalk in the 8×10 Gbit/s OTDM system using SMZ switch

Optical time division multiplexing is an emerging and promising alternative for future high-speed photonic networks because of its ability to accommodate higher bit rate and flexible bandwidth. Symmetric Mach–Zehnder (SMZ) have been found to be the most suitable switching element than all the available de-multiplexing switches because of compact size, thermal stability, and low-power operation. In this paper, we simulate eight-channel OTDM systems (all-channel multiplexer and de-multiplexer (DEMUX)) with a Mach–Zehnder modulator and SMZ de-multiplexer to investigate the impact of control signal power and to calculate the crosstalk.     

The width of the rotational contour of vibrational and vibronic bands of complex molecules in the gas phase as a temperature indicator

From the independence of the contour of spectral density of the rotational (orientation) correlation function of a rigid molecular top of arbitrary symmetry on temperature in the frequency scale based on the reduced time of rotational orientation relaxation and from the near independence of the rotational contour of vibrational and vibronic absorption bands of dipole transitions in the same coordinates in a model of “regular diffusion” of the transition oscillator with a classically rotating rigid molecular top, it is suggested that it is possible to use the halfwidth of the contour for estimation of temperatures. Data are presented on the halfwidth of 48 contours of bands of A, B, and C types at this frequency for 12 compounds for a temperature range of from units to 500 degrees of absolute temperature measured experimentally and (for low temperatures) calculated by the quantum theory. Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 3, pp. 312–317, May–June, 1997.     

Spectra and structure of energy levels of Pr3+ in crystals of yttrium and gadolinium oxyorthosilicates

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 6, pp. 123–129, November–December, 1995.     

Comparison of Theoretical Methods and Basis Sets for ab initio and DFT Calculations of the Structure and Frequencies of Normal Vibrations of Polyatomic Molecules

The dependence of the quality of calculation of the geometric parameters and frequencies of normal vibrations on the choice of the theoretical method and the basis set of Gaussian functions has been investigated within the framework of four approximations (DFT/B3LYP, HF, MP2, MP3), using benzene and s-triazine molecules as an example. It has been shown that the molecular parameters calculated using the basis set without polarization functions within the framework of any of the above theoretical methods agree poorly with the experimental data. It has been concluded that the use of the basis set 6-31G(d) within the framework of these methods with allowance for the electron correlation for calculating the geometric parameters and frequencies of normal vibrations of polyatomic cyclic compounds is most optimum in terms of the relation between the expenditure of time and the quality of the calculation. The coefficients of linear scaling of frequencies have been obtained by the DFT/B3LYP method for 22 basis sets that were tested on porphin, pyrrole, indene, and pyridine molecules. Atypically large errors in determining the frequencies of some benzene and s-triazine vibrations have been obtained in a number of quantum-mechanical calculations with large basis sets. The changes in the force field for these cases have been investigated with the example of the benzene molecule.     

Luminescent methods in the chemistry of lanthanides

The work was reported at the International Conference on Luminescence in Moscow in November 1994.     

Spectral-luminescence and lasing properties of several morpholine derivatives of naphathalimide in different solvents

The spectral-luminescence properties, lasing ability, and time-resolved gain spectra of three morpholine derivatives of naphthalimide (substituted in position 4) in polar (ethanol and dimethylformanide) and nonpolar (diethyl ester and toluene) solvents are investigated. It is found that rotation of the morpholine group about the single bond connecting the group with the rest molecule takes place, which results in a shift of the gain spectrum towards the longwave region and decrease of the fluorescence quantum yield. Deceased. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 603–606, September–October, 1997.