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The determination of molecular parameters from dielectric measurements on nematic liquid crystals
No full textbThe physical properties of liquid crystal phases (mesophases) depend in a very sensitive manner on the structure of the constituent liquid crystal-forming molecules (mesogens). Thus a small change in molecular structure can result in a dramatic change in the corresponding liquid crystal properties. The dielectric responses of materials reflect the electric properties of molecules, and so analysis of dielectric measurements on liquid crystals in terms of molecular properties should lead to the development of structure/property relationships for such mesophases. This paper explores the problems of determining molecular parameters from dielectric measurements on nematic liquid crystals. Specifically, the difficulties in defining the internal electric field and knowing the value of the order parameter are addressed. Experimental results on a range of liquid crystals show that short range correlations are important in determining both the dielectric and optical response of nematic liquid crystals. It is concluded therefore that more sophisticated molecular theories, which take account of molecular shape and volume, need to be developed before reliable structure/property relationships can be established for liquid crystals
On the investigation of field-induced director dynamics: a novel ESR experiment
No full textThe rotational viscosity coefficient of a nematic liquid crystal with a positive diamagnetic susceptibility anisotropy can be determined by monitoring the time dependence of the director orientation as it is rotated by a field from a non-equilibrium to the equilibrium state parallel to the field. A variety of techniques is available using different properties to monitor the director orientation as a function of time. Normally these experiments are designed so that the property used to determine the director orientation does not change during the time taken for its measurement. Here using ESR spectroscopy, we explore the benefits of exploiting exactly the opposite situation. That is during the time taken to record the ESR spectrum the director orientation is allowed to change. We have developed both semi-quantitative and quantitative models to allow us to simulate how the form of the spectrum depends on experimental conditions such as the field scan rate. These models have also proved to be valuable in designing the experiment and in analysing the spectra. It seems that this novel ESR experiment provides a valuable route to the field-induced relaxation time and hence to the rotational viscosity coefficient
Flexible dimers as dopants for liquid crystal display mixtures with faster relaxation times
No full textA series of fluoro-substituted ?,?-bis-diphenyloxyalkanes have been investigated as possible dopants for nematic liquid crystal display mixtures to reduce the rotational viscosity and hence response times of the mixtures. The compounds have been prepared using the Williamson synthesis, and the effect of the dopants on the mesophase transition temperature of a suitable Merck display mixture host ( ZLI-4792) has been determined. Measurements of magnetic field-induced relaxation times for director reorientation have been made on the doped and undoped mixtures using a novel electron spin resonance ( ESR) method developed by some of the authors. The relationship between field-induced relaxation times and the rotational viscosity is explained and results are reported for the rotational viscosity of the host material. A brief discussion of the molecular theories of rotational viscosity of nematic liquid crystals identifies the important molecular factors as shape, size, flexibility and orientational order parameter. The influence of the dopant molecules on the orientational order parameter of the doped mixtures has been measured using a static ESR method, and these results enable the separate effects of the dopants on the order parameter of the host and on the rotational dynamics to be identified. Results for field-induced relaxation times and order parameters of doped mixtures are reported for seventeen ?,?-bis-fluoro-diphenyloxyalkane dopants. Additionally comparative results are reported for a structurally related compound 1,2-trans-di(4'-propylphenyl) 1',2'- difluoroethane. It is found that particular substitution patterns of fluorine atoms in the phenyl rings of the dopant compounds can result in shorter relaxation times for the nematic display mixture investigated. The use of flexible dimers as dopants provides an additional design aid in the development of nematic mixtures for applications
The phase behavior of a binary mixture of rodlike and disclike mesogens: Monte Carlo simulation, theory, and experiment
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Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Molecular theory of dielectric relaxation in nematic dimers
No full textThis paper reports a theory for the dielectric relaxation of dimeric mesogenic molecules in a nematic liquid crystal phase. Liquid crystal dimers consist of two mesogenic groups linked by a flexible chain. Recent experimental studies [D. A. Dunmur, G. R. Luckhurst, M. R. de la Fuente, S. Diez, and M. A. Perez Jubindo, J. Chem. Phys. 115, 8681 (2001)] of the dielectric properties of polar liquid crystal dimers have found unexpected results for both the static (low frequency) and variable frequency dielectric response of these materials. The theory developed in this paper provides a quantitative model with which to understand the observed experimental results. The mean-square dipole moments of alpha, omega-bis[(4-cyanobiphenyl-4'-yl]alkanes in a nematic phase have been calculated using both the rotational isomeric state model and a full torsional potential for the carbon-carbon bonds of the flexible chain. The orienting effect of the nematic phase is taken into account by a parametrized potential of mean torque acting on the mesogenic groups and the segments in the flexible chain. Results of calculations using the full torsional potential are in excellent agreement with experimental results for comparable systems. The probability density p(eq)(beta(A),beta(B)) for the orientation of the mesogenic groups (A,B) along the nematic director is also calculated. The resultant potential of mean torque is a surface characterized by four deep energy wells or sites equivalent to alignment of the terminal groups A and B approximately parallel and antiparallel to the director; of course, the reversal of the director leads to equivalent sites. This potential energy surface provides the basis for a kinetic model of dielectric relaxation in nematic dimers. Solution of the Fokker-Planck equation corresponding to this four-site model gives the time dependence of the site populations, and hence the time-correlation functions for the total dipole moment along the director. In this model the end-over-end rotation of the molecule, corresponding to simultaneous reversal of both mesogenic groups, is excluded because the activation energy is too large. Results are presented for a number of cases, in which a dipole is located on one or both of the mesogenic groups, and additionally where the groups differ in size. For the latter, under particular conditions, the correlation function exhibits a biexponential decay, which corresponds to two low frequency absorptions in the dielectric spectrum. This is exactly what has been observed for nonsymmetric nematic dimers having different groups terminating a flexible chain. Experimental results over a range of temperature for the nonsymmetric dimer alpha-[(4-cyanobiphenyl)-4'-yloxy]-omega-(4-decylanilinebenzylidene-4'-o xy)nonane can be fitted precisely to the theory, which provides new insight into the orientational and conformational dynamics of molecules in ordered liquid crystalline phases
Torsional elasticity for mesophases
No full textFocuses on the torsional elasticity for mesophases as a property of liquid crystals
Variations on the Author
Full text link“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
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