Measurement of Translational Diffusion in Nematics

Measurement of translational diffusion in nematics CLASSICAL EXPERIMENTAL METHODS... 

The direct NMR method for determining translational difiFusion constants in liquid crystals was described previously. The indirect NMR methods involve measurements of spin-lattice relaxation times (Ti,Ti ),Tip) [7.45]. Prom their temperature and frequency dependences, it is hoped to gain information on the self-diflPusion. In favorable cases, where detailed theories of spin relaxation exist, difiFusion constants may be calculated. Such theories, in principle, can be developed [7.16] for translational difiFusion. However, until recently, only a relaxation theory of translational difiFusion in isotropic hquids or cubic solids was available [7.66-7.68]. This has been used to obtain the difiFusion correlation times in nematic and smectic phases [7.69-7.71]. Further, an average translational difiFusion constant may be estimated if the mean square displacement is known. However, accurate determination of the difiFusion correlation times is possible in liquid crystals provided that a proper theory of translational difiFusion is available for liquid crystals, and the contribution of this difiFusion to the overall relaxation rate is known. In practice, all of the other relaxation mechanisms must first be identified and their contributions subtracted from the observed spin relaxation rate so as to isolate the contribution from translational difiFusion. This often requires careful measurements of proton Ti over a very wide frequency range [7.72]. For spin - nuclei, dipolar interactions may be modulated by intramolecular (e.g., collective motion, reorientation) and/or intermolecular (e.g., self-diffusion) processes. Because the intramolecular (Ti ) and intermolecular... 

Proton, deuteron and carbon spin relaxation measurements of liquid crystals have provided detailed information about the molecular motions of such anisotropic liquids (anisotropic rotation and translation diffusion of individual molecules), and about a peculiar feature of liquid crystalline phases, namely collective molecular reorientations or order fluctuations. Spin relaxation in liquid crystalline mesophases has challenged NMR groups since the early 1970s, shortly after the publication of theoretical predictions that order fluctuations of the director (OFD, OF), i.e. thermal excitations of the long-range orientational molecular alignment (director), may play an important unusual role in nuclear spin relaxation of ordered liquids. Unique to these materials, which are composed of rod-like or disc-like (i.e. strongly anisotropic molecules), it was predicted that such thermal fluctuations of the director should, at the frequencies of these fluctuation modes, produce rather peculiar Ti(p) dispersion profiles. For example in the case of uniaxial nematic... 

This section describes both dynamics studies at the molecular level and also cooperative bulk macroscopic properties as sensed by diffusion studies. The measurements of the proton spin-lattice relaxation time of liquid crystal 4- -octyl-4 -cyanobiphenyl (8CB) confined in randomly oriented untreated porous glass have been presented. The studies are in agreement with the model of mutually independent pores with nematic director parallel to the pore axis in each segment. The local translational diffusion of molecules within the cavities is found to be nearly as fast as in bulk. Orientational relaxation of a model discotic liquid crystal, consisting of dislike molecules... 

Incoherent quasi-elastic neutron scattering (IQENS) has been used to investigate the dynamics of nematic phases. When a monochromatic beam of neutrons is scattered from a nematic liquid crystal the shape of the elastic line in the energy-transfer spectra gives information on the molecular dynamics. A quasi-elastic neutron scattering measurement may be used to investigate the diffusive motions of the molecules in the nematic phase. The translational diffusion coefficients may be determined and localised motions such as molecular rotation and internal rotations may also be characterised. 

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