Anisotropic self-diffusion in thermotropic liquid crystals studied by 1H and 2H pulse-field-gradient spin-echo NMR.

The molecular self-diffusion coefficients in nematic and smectic-A thermotropic liquid crystals are measured using stimulated-echo-type 2H and 1H pulse-field-gradient spin-echo nuclear magnetic resonance (PGSE NMR) combined with multiple-pulse dipolar decoupling and slice selection. The temperature dependence of the principal components of the diffusion tensor in the nematic phase follows a simple Arrhenius relationship except in the region of nematic-isotropic phase transition where it reflects, merely, the decrease of the molecular orientational order. The average of the principal diffusion coefficients in the isotropic-nematic phase transition region is close to the diffusion coefficient in the isotropic phase. At the nematic-smectic-A phase transition the diffusion coefficients change continuously. The results in nematic phase are best described in terms of the affine transformation model for diffusion in nematics formed by hard ellipsoids. In the smectic-A phase the data are interpreted using a modified model for diffusion in presence of a periodic potential along the director.

Molecular self-diffusion in a columnar liquid crystalline phase determined by deuterium NMR.

We report translational diffusion coefficients in a columnar phase of a discotic liquid crystal formed by a triphenylene-based compound. The experiments were performed using 2H stimulated-echo-type pulsed-field-gradient spin-echo NMR applied to a chain-deuterated sample. The diffusion coefficients were found in the range of 1x10(-14)-4x10(-14) m2/s, three orders of magnitude lower than in the isotopic phase of the same compound. This, together with the high activation energy obtained in columnar phase, indicates that the diffusion is dominated by solidlike jump processes.

Deuterium stimulated-echo-type PGSE NMR experiments for measuring diffusion: application to a liquid crystal.

The accessibility of molecular self-diffusion coefficients in anisotropic materials, such as liquid crystals or solids, by stimulated-echo-type (2)H PGSE NMR is examined. The amplitude and phase modulation of the signal in the stimulated-echo-type sequence by the static quadrupole coupling during the encoding/decoding delays is suppressed by adjusting the pulse flip angles and the phase cycle. For nuclei that experience both nonnegligible quadrupole and dipole couplings, the application of magic echoes during the evolution periods of stimulated echo is demonstrated as a helpful technique in the case of slow diffusion. These findings are demonstrated by experimental results in the thermotropic liquid crystal of partially deuterated 8CB. The obtained diffusion coefficients are also compared to data obtained by a (1)H homonuclear-decoupling-type PGSE NMR method in the same material.

Conformational investigation of a cyclic enterobacterial common antigen employing NMR spectroscopy and molecular dynamics simulations.

The three-dimensional structure of a cyclic enterobacterial common antigen (ECA) having four trisaccharide repeating units has been investigated by NMR spectroscopy and molecular dynamics simulations. Three different NMR parameters were determined: (a) (1)H,(1)H cross-relaxation rates from NOE experiments were used for determination of proton-proton distances; (b) trans-glycosidic (3)J(C,H) scalar coupling constants analyzed via a Karplus-type relationship provided information on torsion angles; and (c) (1)H,(13)C one-bond dipolar couplings obtained in a dilute liquid-crystalline medium were interpreted in terms of the orientational order and molecular conformations. The molecular dynamics simulations of the dodecasaccharide were performed with explicit water and counterions, which are important factors that strongly influence molecular conformation. Subsequently, the results from computer simulation were used to generate a three-dimensional structure of the cyclic ECA which is consistent with the experimental NMR parameters.

Rotational viscosity in a nematic liquid crystal: a theoretical treatment and molecular dynamics simulation.

The rotational viscosity coefficient gamma(1) of 4-n-pentyl-4(')-cyanobiphenyl in the nematic phase is investigated by combination of existing statistical-mechanical approaches (SMAs), based on a rotational diffusion model and computer simulation technique. The SMAs rest on a model in which it is assumed that the reorientation of an individual molecule is a stochastic Brownian motion in a certain potential of mean torque. According to the SMAs, gamma(1) is found to be a function of temperature, density, rotational diffusion coefficient, and a number of order parameters (OPs). The diffusion coefficient and the OPs were obtained from an analysis of a trajectory generated in a molecular dynamics simulation using realistic atom-atom interactions. In addition, a set of experimentally determined diffusion coefficients and OPs was used for evaluation of gamma(1). Reasonable agreement between calculated and experimental values of gamma(1) is obtained. It is shown that near the clearing point gamma(1) is proportional to (-)P22, where (-)P2 is the second-rank OP. This limiting value of gamma(1) is in agreement with mean-field theory.

Statistical-mechanical study of the pair correlations for the dipolar Gay-Berne model.

A statistical-mechanical theory based upon the method of conditional distribution function has been applied to calculations of the nearest-neighbor (NN) and next NN correlators as well as order parameters. The method takes into account translational and orientational correlations as well as their coupling. Using the dipolar Gay-Berne interaction potential, calculations have been carried out for temperatures and densities corresponding to a nematic phase. The results in orientational distribution functions indicate a significant effect of the dipole-dipole interactions on the orientational order of the liquid crystal. It was found that NN particles tend to be mutually antiparallel, whereas a reversed tendency is observed for next NN particles. These results are in agreement with computer simulations and with interpretations of experimental data.