The influence of rotational depolarization on the mechanism of energy transport in two-component systems: The nature of correlations

The correlation effect in two-component systems of different viscosities was analyzed based on a concentration depolarization experiment. The inclusion of a correlation effect was found to be fully justified only in systems for which the localization time, _l, is considerably shorter than that of the rotational relaxation, _rot. On the grounds of an approximate analysis, taking into account the competition between the concentration and the rotational depolarization, it was possible to explain the concentration changes in the emission anisotropy in the systems investigated.Dedicated to Professor Czestaw Bojarski on the occasion of his 70th birthday.     

Thermally stimulated depolarization currents of films obtained from supernatant layer of mixed solutions of stereoregular polymethyl methacrylates

Summary Thermally stimulated depolarization currents were investigated for films obtained from supernatant layer of mixed solutions ofi- ands-PMMA ini/s weight ratio of 1/1 and 1/2. The results showed that the degree of stereocomplex formation is not uniform: the mixed solutions contain the insoluble and the soluble stereocomplex aggregates and in some case the residual (free)i-PMMA. The stereocomplex is formed ini/s weight ratio of 1/2.     

Survival of molecular information under surfaced‐enhanced resonance Raman (SERRS) conditions

In the present paper, we discuss the molecular information that can be derived from surface‐enhanced resonance Raman Scattering (SERRS) experiments performed with different excitation wavenumbers, which are close to resonance with an excited electronic state of the molecule [surface‐enhanced Raman dispersion spectroscopy (SERADIS)]. We specifically consider the situation, where a molecule is physisorbed to a site characterized by a local electric field with a direction independent of the direction of the external, exciting field. The molecular information available in this experimental situation is compared with the information available in a corresponding Raman dispersion spectroscopy (RADIS) experiment performed on a free molecule or a molecule physisorbed to a site, where the local field is isotropic. The consequences for resonance Raman scattering (RRS) and RADIS, when the molecule is adsorbed in the highly anisotropic hot spot (HS), are discussed; here it is shown that only the molecular information originating from the symmetric part of the scattering tensor can survive in SERRS and in SERADIS. Besides, it is shown that the depolarization ratio can no longer be used to discriminate between totally and non‐totally symmetric modes in the polarized surface‐enhanced Raman scattering (SERS) spectra. These results have implications for the resonance Raman spectra, but even more important for the application of the resonance Raman effect in the investigation of excited vibronic molecular states, in general, and in the investigation of electronic states in larger bio‐molecules, such as the various metallo‐porphyrins. Copyright © 2009 John Wiley & Sons, Ltd.     

A DFT and MP2 Study on the Molecular Structure and Vibrational Spectra of Halogenosubstituted Phosphoryl and Thiophosphoryl Compounds

The molecular geometrical parameters, rotational constants, dipole moments and vibrational infrared properties of a series of phosphoryl compounds (OPX _i Y _j Z _k , X, Y, Z = F, Cl, Br; i+ j + k = 3) and their thio analogs are predicted by density functional and MP2 calculations using the 6-311G(2d,2p) basis set. Both methods yielded similar results. The predicted molecular parameters and the vibrational Raman and infrared spectra agree well with the available experimental data. The Raman Scattering Activities (RSA) and depolarization ratios (Dep) of the molecules are obtained by DFT calculations. Considering the different substitution modes of various halogen atoms, the resultant changes in the geometrical and vibrational properties are discussed. Such studies permit detailed information to be obtained concerning unknown molecules and can define the guidelines for synthesizing molecules of particular characteristics.     

Polymer chain conformation in the phase separation process of a binary liquid mixture

A polymer chain conformation change near the critical point of liquid-liquid phase separation was investigated. Poly(N-isopropylacrylamide) labeled with a small amount of carbazolyl group for a fluorophore (P(NIPA-Cz)) was prepared. A ternary system of P(NIPA-Cz)+cyclohexane+methanol was investigated by the fluorescence spectroscopic technique. A mixed solvent of cyclohexane+methanol (CH/MeOH) shows phase separation at the upper critical solution temperature. Light scattering intensity, fluorescence emission intensity and fluorescence anisotropy ratio, as a function of temperature, were measured with quasi statically approaching to the critical demixing point. The fluorescence intensity of the carbazolyl groups attached to the polymer chain decreases with approaching to the critical temperature. This result suggests that the radius of gyration of the polymer decreases upon approaching to the critical demixing point of the solvent. We discuss the collapse and aggregation processes of the polymer based on the fluorescence quenching method. The rotational diffusion coefficient of carbazolyl groups attached to the polymer chain was estimated by the fluorescence depolarization technique. The rotational motion of carbazolyl groups is slowed down upon approaching the critical point.     

Transient and thermally stimulated depolarization currents in pure and iodine doped polyvinyl formal (PVF) films

Transient currents, measured with pure and iodine doped polyvinyl formal (PVF) films as a function of poling field (15–100 kV/cm) and temperature (30–95°C), have been found to follow Curie-von Schweidler law characterized with two slopes in short and long time regions. The isochronals (i.e. current/temperature plots at constant times) have been found to give rise to a peak located at 75°C. The order of current has been found to increase with increase in poling field, temperature and iodine mixing. The comparative studies of the isochronals with the thermally stimulated discharge current (TSDC) indicated the strong resemblance between the two studies. It is suggested that both the dipolar orientation due to molecular mechanism of motions with the side chains and space charge due to trapping of injected charge carriers in energetically distributed traps may be responsible for the observed currents. The dependence of current and activation energy on iodine mixing is explained on the basis of a charge transfer type of interaction.     

Efficiency of second harmonic generation for partially coherent light in anisotropic crystals

This paper analyzes the second harmonic generation (SHG) efficiency of light with partial temporal coherence due to depolarization effects in birefringent media. It discusses relations between SHG efficiency fading, light source spectrum, crystal birefringence, and phase matching conditions. The efficiency of SHG pumped by the partially coherent light beam that may depolarize light in nonlinear birefringent crystal is also analyzed. The basic theory of SHG with its modification for partially coherent light with depolarization and some numerical calculations of the SHG process are described. Presented at 9-th International Workshop on Nonlinear Optics Applications, NOA 207, May 17–20, 2007, Świnoujście, Poland     

Multiple scattering of muons in beryllium

The defocussing and the depolarization of a high energy muon beam in a beryllium filter, often used to eliminate accompanying pions, have been studied. The quantum mechanical transport equation of Waldmann, which can also be used to describe the multiple scattering of Dirac particles, is solved with a distorted wave Born approximation. Calculations are done for both the Thomas-Fermi and the Hartree-Fock potential of the beryllium atom. It is shown that the Hartree-Fock potential leads to a less divergent beam. The depolarization of a longitudinally polarized muon beam in passage through a thin beryllium foil is also studied.     

Thermally stimulated depolarization current spectra of cross-linked polyethylene and the influence of cross-linking byproducts

Cross-linked polyethylene (XLPE) is notable for its use as power cable insulation. Its longevity is limited by space charge buildup linked to impurities such as the byproducts left behind by the cross-linking agent dicumyl peroxide (DCP). The goal of this work is to determine the impacts of these byproducts on charge trapping and detrapping in XLPE using the thermally stimulated depolarization current technique. XLPE with byproducts has one source of trapped charge, which originates from the byproducts. XLPE that was thermally treated via degassing exhibits two other sources of trapped charge, which are charge injection and dipolar relaxations. Oxidation from degassing was shown to control the trapping from these sources, which is useful knowledge for processing this material prior to its use. Reintroducing acetophenone, one of the major byproducts of DCP, suppresses those two peaks once more, showing that it controls the overall space charge buildup characteristics in XLPE.