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1.
In this work, the electro-optic response of a 6CB liquid crystal layer is studied using a sensitive differential technique. The layer is held at a temperature just above the nematic to isotropic phase transition. Transverse magnetic (p) polarized light incident on the cell is coupled to guided modes in the liquid crystal layer using prism coupling. The modes manifest themselves as sharp dips in the reflectivity as the angle of incidence is scanned. When a low frequency sinusoidal voltage is applied to the cell, the resonant mode shapes and excitation angles are altered at a frequency which is twice that of the applied field, resulting in a modulation of the reflectivity for a given angle of incidence. By synchronous observation of the modulated signal, a differential signal is recorded. Comparing the data with modelling generated from multilayer optics theory, two effects are then quantified. The first of these is an induced birefringence, varying quadratically with applied voltage, which is well understood and can be expressed in terms of Landau-de Gennes theory. The second is a field induced perturbation in the imaginary part of the optical permittivity, δεi, which implies a modification of the light scattering properties of the liquid crystal. The measurement of the latter effect is, as far as we know, a novel one, being only made possible by the remarkable sensitivity of the synchronous differential technique. 相似文献
2.
This article explores the impact of the multipolar distribution on chiral discrimination in a series of racemic fluids. Discrimination is measured via the difference between the like-like (LL) and the like-unlike (LU) radial distributions in the liquid. We have found previously that the magnitude and orientation of the molecular dipole have a decisive impact on the short-ranged enantiomeric imbalance in racemates. Although quadrupolar and octupolar interactions decrease more rapidly with intermolecular separation, they can be significant at small separations, where enantiomeric imbalances occur. We have carefully selected a number of models in which we isolate the effects of the molecular quadrupole and octupole. We find that discrimination can be greatly enhanced by changes in the quadrupole moments. However, for octupole moments, changes in discrimination are small and some octupoles inhibit discrimination. We identify the quadrupole moment closest to the plane perpendicular to the direction of the molecular dipole as the moment that has the greatest favorable effect on chiral discrimination in racemates. In racemates where this moment is large, we have found differences of up to 40% between the LL and the LU radial distributions. 相似文献
3.
Wanwilai Chaisan Rattikorn Yimnirun David P. Cann 《Journal of solid state chemistry》2005,178(3):613-620
The electrical properties of ceramics within the TiO2-SnO2 system which exhibit spinodal decomposition were investigated under different annealing conditions. Changes in the lattice parameter and the phase evolution of the spinodal decomposition, measured in terms of the volume fraction transformed X(t), were examined as a function of annealing time using X-ray diffraction. The room temperature dielectric properties were measured and compared to dielectric mixing rules. Doping with pentavalent Nb was found to slow the decomposition kinetics and a high permittivity (εr>1000) was induced. The origin of the high permittivity is linked to the formation of an electrically heterogeneous structure which is derived from the spinodal microstructure. Lastly, it was observed that Nb-doped TiO2-SnO2 ceramics exhibited non-linear current-voltage behavior which can be attributed to the negative temperature coefficient of resistance effect. 相似文献
4.
John W.Grove 《数学物理学报(B辑英文版)》2010,30(2):563-594
This article describes mathematical models for phase separated mixtures of materials that are in pressure and velocity equilibrium but not necessarily temperature equilibrium. General conditions for constitutive models for such mixtures that exhibit a single mixture sound speed are discussed and specific examples are described. 相似文献
5.
A theoretical study of the solvation of ( R)- N-(3,5-dinitrobenzoyl)phenylglycine- and ( R)- N-(3,5-dinitrobenzoyl)leucine-derived chiral stationary phases (CSPs) is presented. Semiflexible models of the chiral selectors are prepared from B3LYP/6-311G** calculations, and these are used in the molecular dynamics simulations of the corresponding interface. The chiral interface is examined for four solvents: 100% hexane, 90:10 hexane:2-propanol, 80:20 hexane:2-propanol, and 100% 2-propanol. Despite the similarities between phenylglycine and leucine, the interfaces are distinct both in terms of the selector orientations at the surface and in the number of hydrogen bonds formed with 2-propanol. We also find that an increase in alcohol concentration alters the preferred orientations of the selectors. 相似文献
6.
A solvation shell may adapt to the presence of a chiral solute by becoming chiral. The extent of this chirality transfer and its dependence on the solute and solvent characteristics are explored in this article. Molecular dynamics simulations of solvated chiral analytes form the basis of the analysis. The chirality induced in the solvent is assessed based on a series of related chirality indexes originally proposed by Osipov [M. A. Osipov et al., Mol. Phys. 84, 1193 (1995)]. Two solvents are considered: Ethanol and benzyl alcohol. Ethanol provides insight into chirality transfer when the solvent interacts with the solute primarily by a hydrogen bond. Several ethanol models have been considered starting with a nonpolarizable model, progressing to a fluctuating charge model, and finally, to a fully polarizable model. This progression provides some insights into the importance of solvent polarizability in the transfer of chirality. Benzyl alcohol, by virtue of the aromatic ring, increases the number of potential solvent-solute interactions. Thus, with these two solvents, the issue of compatibility between the solvent and solute is also considered. The solvation of three chiral solutes is examined: Styrene oxide, acenaphthenol, and n-(1-(4-bromophenyl)ethyl)pivalamide (PAMD). All three solutes have the possibility of hydrogen bonding with the solvent, the last two may also form ring-ring interactions, and the last also has multiple hydrogen bonding sites. For PAMD, the impact of conformational averaging is examined by comparing the chirality transfer about rigid and flexible solutes. 相似文献
7.
P.M. Jones P.A. Butler K.J. Cann J.F.C. Cocks G.D. Jones R. Julin H. Kankaanpää W. Pohler B. Schulze J.F. Smith A.N. Wilson 《Zeitschrift für Physik A Hadrons and Nuclei》1997,358(2):191-192
Conversion electron studies of medium-heavy to heavy nuclear mass systems are important where the internal conversion process begins to dominate over gamma-ray emission. The use of a segmented detector array sensitive to conversion electrons has been used to study multiple conversion electron cascades from nuclear transitions. The application of the Silicon Array for ConveRsion Electron Detection (SACRED) for in-beam measurements has successfully been implemented. 相似文献
8.
Brendan Mc Cann 《Annali di Matematica Pura ed Applicata》1990,157(1):27-61
Summary
We present a Fitting Class construction which exploits the properties of a certain class of finite soluble groups of nilpotent length three, called
-groups in the paper. In addition we look at a wider class of groups, called
in the paper, also of nilpotent length three and examine the question as to what
-groups are in
.A number of examples are given to illuminate the various classes.The author would like to thank HermannHeineken for supervising his dissertation, from which this paper has sprung, the German Academic Exchange Service (DAAD) for enabling him to study with Prof. Heineken at Universität Würzburg and An Roinn Oideachais for the fellowship which is at present supporting him at University College, Galway. 相似文献
9.
Racemic fluids of chiral calamitic molecules are investigated with molecular dynamics simulations. In particular, the phase behavior as a function of density is examined for eight racemates. The relationship between chiral discrimination and orientational order in the phase is explored. We find that the transition from the isotropic phase to a liquid crystal phase is accompanied by an increase in chiral discrimination, as measured by differences in radial distributions. Among ordered phases, discrimination is largest for smectic phases with a significant preference for heterochiral contact within the layers. 相似文献
10.
Frederick J. Karol Sun-Chueh Kao Kevin J. Cann 《Journal of polymer science. Part A, Polymer chemistry》1993,31(10):2541-2553
High-activity titanium- and vanadium-based catalysts for ethylene polymerization frequently show an increase in reaction rate in the presence of an α-olefin. The magnitude of this increase depends on the specific α-olefin. The results show propylene > 1-butene > 1-hexene in increasing initial reaction rates. Addition of certain electron-donor compounds to these catalysts can lower the magnitude of the comonomer effect and, in some cases, totally eliminate such an effect. Among the classes of electron-donor compounds examined were ether-alcohols, ether-esters, amino-alcohols, alkoxysilanes, siloxanes, and phosphine oxides. Reaction kinetics show that the presence of a comonomer can influence the kinetic order of the reaction. These results can be interpreted using a mechanistic model involving two vacant coordination positions at the active sites. In this model electron donors and comonomers are viewed as Lewis-base ligands which influence features of chain propagation and chain termination. As Lewis-base ligands, the comonomers can also increase the number of active sites available for polymerization. Catalyst deactivation following the initial comonomer rate increase is believed to be caused by reaction with the Lewis bases (α-olefin included) in the system and by possible reduction in the oxidation state of the metal centers. The most acidic metal centers activated by the comonomer are most reactive to Lewis bases and deactivate most rapidly. Veratrole (1,2-dimethoxybenzene) can be employed as a probe for estimating the number of bis-vacant coordination sites in vanadium-based catalysts. Addition of low levels of veratrole led to significant deactivation of the vanadium-based catalyst. © 1993 John Wiley & Sons, Inc. 相似文献