Collisional Relaxation of Luminescence Anisotropy in Rarefied Gases in the Condensed Phase

The orientational relaxation of optically induced anisotropy in rarefied gases and at a damped rotation has been investigated. It has been found that the anisotropy relaxation in rarefied gases is described by a reduced kinetic equation depending only on free rotation integrals. The behavior of the integral anisotropy of luminescence for free symmetric and asymmetric top molecules has been elucidated. The law of luminescence depolarization has been obtained for asymmetric top molecules in the Gordon J-diffusion model. It represents the sum of two Stern–Volmer-type dependences, whose relative contribution is determined by the orientation of the dipole moments of transitions with absorption and emission of light in the molecular coordinate system and by the principal moments of inertia of the molecular top. It has been established that in the limit of a strongly damped rotation, kinetic equations of the general form reduce to equations of rotational diffusion. A number of modified diffusion equations correctly describing the contribution of inertial effects to the orientational relaxation of anisotropy have been obtained.     

The dielectric properties of water in its different states of interaction

A tutorial on dielectric (relaxation) spectrometry of liquids is given in this article. Some methods of measuring complex (electric) permittivity spectra are briefly described. Results for water are presented and related to characteristic properties of the liquid structure and to models of the molecular dynamics, particularly as resulting from computer simulation studies. Dielectric spectra for aqueous solutions of low weight electrolytes, polyelectrolytes, small molecules, and polymers are discussed to illustrate effects of kinetic depolarization, structure saturation, as well as positive, negative, and hydrophobic hydration. Reference is also made to fluctuations in the hydrogen bond network of mixtures of water with liquids that are completely miscible with this unique solvent.     

Thermally stimulated depolarization currents of tactic polymethyl methacrylates and their mixtures

Summary Thermally stimulated depolarization currents (TSDC) of atactic (a), syndiotactic (s) and isotactic (i) PMMA and mixtures ofs- andi-PMMA were measured. In pure tactic PMMA, TSDC peak was obtained at a temperature corresponding to the glass transition temperature of each PMMA. TSDC of mixtures isolated as precipitates from 1/1 and 1/2 (i/sweight ratio) mixed solutions showed a peak which can be attributed to the glass transition temperature of the stereocomplex. TSDC of original l/1 mixture showed two peaks which are ascribed to the glass transition temperature of residual i-PMMA and the stereocomplex. The results suggests that stereocomplex formation occurs ini/s weight ratio of 1/2 independent of the way of preparation.With 9 figures and 1 table     

固态热容激光器3维瞬态热畸变模拟分析

根据固态热容激光器的动态工作特性,考虑热力学参数与温度的关系,采用3维有限差分方法模拟分析了薄片热容激光器的3维温度和热应力分布随时间的变化关系。计算了热容激光器的热畸变和退偏损耗随时间的动态变化规律,并与采用连续水冷却方式工作的圆棒激光器的热畸变特性做了比较。模拟结果显示,形变是引起波前相位畸变的主要因素,退偏损耗随泵浦时间增加和泵浦功率增大而非线性增大。     

Depolarization properties of cirrus clouds from polarization lidar measurements over Hefei in spring

A new polarization lidar has been developed for detecting depolarization characteristics of aerosol and cirrus over Hefei (31.90°N, 117.16°E), China. The fundamental principle of polarization lidar is briefly introduced.     

Phase transitions in gallium nanodroplets detected by dielectric spectroscopy

Both theoretical and experimental works give evidence that gallium exhibits solid phases labelled , , , besides the stable phase strongly dependent both on the size and the confinement conditions. An experimental technique was used based on capacitance and conductance measurements vs. temperature in the audiofrequency range. This technique is particularly sensitive to the conditions of the investigated particle surface that plays a fundamental role in the melting and more generally in the phase transition processes. In particular the strict relation between the derivative of the capacitance with respect to the temperature, dC/dT, and the entropy of the system is considered. In gallium nanoparticles 20 nm in radius, only the phase is shown to occur. Further the transition to liquid phase was detected. The melting process was found to start about 65 K below the full melting temperature value. In the case of particles 10 nm in radius, where different metastable phases may occur, the capacitance vs. temperature curve was found to display abrupt changes of the slope. The singularities are associated to a well defined transition temperature.     

Solvation and Solvent Relaxation in Swellable Copolymers as Studied by Time-Resolved Fluorescence Spectroscopy

The fluorescent probe dimethylaminonaphthylsulfonamide is covalently bound to the ends of the pol(ethylene glycol) chains of the swellable block copolymers poly(ethylene glycol)–polystyrene (PEG-PS) and poly(ethylene glycol)–poly(ethylene imine) (PEG-PEI) to investigate the molecular mobility inside the polymers, swollen by different liquids. Steady-state and time-resolved studies of the Stokes shift between absorption and fluorescence spectra reveal that the probe is solvated by both the polymer matrix and the liquid phase. The extent of solvation by the liquid and the mobility of the microenvironment of the probe depend on both the swelling volume of the polymer and the solubility of the probe in this liquid. Steady-state and time-resolved fluorescence depolarisation measurements show that the polymer matrix forms a very rigid solvent cage, which almost completely immobilizes the probe. Upon solvation of the probe by the liquid, the mobility of the probe increases. In PEG-PEI swollen by polar solvents, the mobilities of the probe itself and of its microenvironment, although not reaching the values observed in homogeneous solution, are significantly higher than in PEG-PS, due to the hydrophilic nature of the polymeric backbone in PEG-PEI.     

Assessment of the Nature of Depolarization Current in Thermally Treated Kapton Polyimide

Pyrolysis of normally insulating aromatic polyimide is known to impart electrical conductivity to the polymer due to the formation of carbonized regions in an insulating matrix with a concomitant change in the polymer’s structural arrangement. The wholly pyrolyzed polyimide is potentially useful for specific applications in certain types of semiconductor devices because of the polyimide’s insulator/conductor transition which creates a barrier type conduction. Pyrolysis, however, degrades the required mechanical integrity of the polyimide for construction of such devices. In order to evaluate the fundamental aspects of barrier conduction by high voltage electron transfer from metal contact that can still produce measurable current in thermally treated non-pyrolyzed polyimide, the nature of depolarization in Kapton was assessed by the thermally stimulated depolarization current (TSDC) technique. The results show that thermal treatment of polyimide without pyrolysis and therefore without loss of mechanical integrity offers a viable means of steady electron conduction for semiconductor operation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Local modes of molecular mobility in comb-shaped liquid crystalline ionomers containing alkaline metal ions

Molecular mobility of the comb-shaped copolymer poly(4-[6-(acryloyloxy)hexyloxy]benzoic acid-co-butyl acrylate) and Li- and Rb-containing LC ionomers based on this polymer was studied at low temperatures by the methods of dielectric spectroscopy and thermally stimulated depolarization current. The above copolymers are shown to experience the γ₂, γ₁, and β-processes, which are related by the reorientation of the end СООН groups, by the mobility of a spacer, and by the reorientation of mesogenic fragments (dimers of oxybenzoic acids) with respect to a long axis, respectively. The formation of multiplet structures in ionomers leads to a suppression of the intensity of the β-process that relates with a partial breakdown of hydrogen-bonded dimmers and with a decrease of their molecular mobility.     

Study of the Zn-porphyrin structure by fluorescence spectroscopy methods

Results of investigation of the optical properties of zinc complexes of mesotetraphenylporphyrin and monopyridyltriphenylporphyrin in impurity-free organic solvent are presented. Analyses of absorption and emission spectra and fluoresence decay kinetics in terms of both a sum of exponentials and using simulation of energy-transformation processes in a tetramer-type Zn-porphyrin complex compound are carried out. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 549–552, July–August, 1999.