Molecular Theories for Liquid Crystal Dimers

Although this predicted behavior is qualitatively in accord with that found for dimers it is important to see whether a model based on the synergy between conformational and orientational order can account, at least semiquantitatively, for the unusual properties of liquid crystal dimers. In the next two sections we describe two models which have been proposed and which have been treated using the molecular field approximation. The predictions of the theories are outlined and, where possible, contact is made with experiment. 

During recent decades the molecular theory of flexoelectricity in nematic liquid crystals was developed further by various authors. " In particular, explicit expressions for the flexocoefiicients were obtained using the molecular-field approximation taking into account both steric repulsion and attraction between the molecules of polar shape. The influence of dipole-dipole correlations and molecular flexibility was later considered. Recently flexoelectric coefficients have been calculated numerically using the mean-field theory based on a simple surface intermolecular interaction model. This approach allows us to take into consideration the real molecular shape and to evaluate the flexocoefiicients for mesogenic molecules of different structures including dimers with flexible spacers. 

Reis et al. report theoretical studies of the urea250 and benzene251 crystals. Their calculations start from MP2 ab initio data for the frequency-dependent molecular response functions and include crystal internal field effects via a rigorous local-field theory. The permanent dipolar fields of the interacting molecules are also taken into account using an SCF procedure. The experimental linear susceptibility of urea is accurately reproduced while differences between theory and experiment remain for /2). Hydrogen bonding effects, which prove to be small, have been estimated from a calculation of the response functions of a linear dimer of urea. Various optoelectronic response functions have been calculated. For benzene the experimental first order susceptibility is accurately reproduced and results for third order effects are predicted. Overall results and their comparison with studies of liquid benzene show that for compact nonpolar molecules environmental effects on the susceptibilities are small. 

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