Orientational fluctuations, below

Quasielectric Light Scattering and Order Fluctuations in the Isotropic Phase 174 Nuclear Magnetic Resonance and Order Fluctuations in the Isotropic Phase. 175 Quasielastic Light Scattering and Orientational Fluctuations below Tc. . . 177 Nuclear Magnetic Resonance and Orientational Fluctuations below Tc.. .. 177 Optical Kerr Effect and Transient Laser-Induced Molecular Reorientation.. 181... 

Nuclear Magnetic Resonance and Orientational Fluctuations below... 

Quasielastic Light Scattering and Orientational Fluctuations below Tc. .. 177... 

The x-ray results presented here show both consistencies and discrepancies with NMR observations. The most serious discrepancy is the implied coexistence of static and mobile C nuclei well below our Tc, deduced from the NMR observation of superposed motionally narrowed and powder pattern signals at temperatures as low as 140 K. On the other hand, a minimum in 7 i at 233 K is observed in one NMR experiment. In fact, the two techniques probe different aspects of the structure. NMR experiments to date cannot distinguish between free rotation and jump rotational diffusion between symmetry-equivalent orientations. X-ray diffraction is sensitive to orientational order (as a canonical average of snapshots) even in the presence of substantial thermal disorder, as long as one set of orientations is statistically preferred and the orientational order is long range. Indeed, our measurements indicate that much of the sc order is reduced by orientational fluctuations at Tc. 

The fluctuations in the magnitude of the nematic order parameter are reduced in importance as long range orientational ordering takes place below T. The effect of these fluctuations on Tf in the nematic phase has been discussed by Freed [133]. The fluctuations in the magnitude of the nematic ordering are for T[Pg.1159]

In principle, it is possible to obtain ECC in the absence of molecular orientation if the crystallization is carried out very slowly at high temperatures close to the melting temperature. Thus, Mandelkern obtained polyethylene crystals similar to ECC in their thermodynamic characteristics by a 40 days crystallization of an isotropic melt28. These experiments also characterize one of the possible paths of the generation of order in polymers order through fluctuations 29 (see below). 

As indicated, the power law approximations to the fS-correlator described above are only valid asymptotically for a —> 0, but corrections to these predictions have been worked out.102,103 More important, however, is the assumption of the idealized MCT that density fluctuations are the only slow variables. This assumption breaks down close to Tc. The MCT has been augmented by coupling to mass currents, which are sometimes termed inclusion of hopping processes, but the extension of the theory to temperatures below Tc or even down to Tg has not yet been successful.101 Also, the theory is often not applied to experimental density fluctuations directly (observed by neutron scattering) but instead to dielectric relaxation or to NMR experiments. These latter techniques probe reorientational motion of anisotropic molecules, whereas the MCT equation describes a scalar quantity. Using MCT results to compare with dielectric or NMR experiments thus forces one to assume a direct coupling of orientational correlations with density fluctuations exists. The different orientational correlation functions and the question to what extent they directly couple to the density fluctuations have been considered in extensions to the standard MCT picture.104-108... 

In the first model, the mnneling electron mainly interacts with the electronic polarization of water ( = 1.88) since tunneling was assumed to be fast in comparison with the orientational response of the dipolar molecules of the liquid. Considering water as a dielectric continuum between a jellium spherical tip and planar substrate yields an effective barrier for tunneling that is about 1 eV lower than that for the vacuum case [95]. This result is consistent with photoemission studies of metal/aqueous interfaces, which reveal electron emission into water at 1 eV below the vacuum level [95-97]. Similar models have been employed to examine the effect of thermal fluctuations on the tunneling current [98-100]. Likewise, a related model assessing the noise associated with the reorientation of adsorbed molecules has been presented [101]. 

Floudas and coworkers [88] investigated the static and kinetic aspects of the order-disorder transition in SI2 and SIB miktoarm stars using SAXS and rheology. At temperatures above the order-disorder transition (ODT) the mean field theory describes the experimental results quite well. Near the ODT, SAXS profiles gave evidence for the existence of fluctuations. Both samples separated into cylindrical microdomains below the ODT. The ODT was determined on shear oriented samples and found, by SAXS, to be 379 K in both cases. This was confirmed by rheology. The discontinuities in SAXS peak intensity and in the storage modulus near the ODT were more pronounced for the miktoarm stars than for the diblocks. The %N values, where % is the interaction parameter and N the... 

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