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In liquid crystals, while the second and fourth rank orientational order parameters characterizing a nematic phase can be experimentally determined via several techniques, there is no straightforward experiment rendering the positional order parameters characterizing a smectic A phase. This work illustrates a novel method to estimate the positional order parameters of a smectogenic liquid crystal solvent from knowledge of the orientational order parameters of a number of solutes dissolved therein. The latter order parameters can be experimentally determined via liquid crystal NMR spectroscopy. These data can be then analyzed with a statistical-thermodynamic density functional theory, whose basic ingredient is a model for solute-solvent intermolecular interactions. Its parametrization and the subsequent fitting procedure eventually permit one to obtain the positional order parameters of the solvent besides the positional-orientational distribution function of the solutes. The method is applied to the smectogen 4,4′-di-n-heptyl-azoxybenzene, in which the solutes 1,4-dichlorobenzene and naphthalene have been dissolved. With the help of this exploratory practical example, pros and cons of the method are pointed out and further developments prospected. [ABSTRACT FROM AUTHOR]

The proton NMR spectra of two 13C-labeled isotopomers of styrene dissolved in two liquid crystalline solvents have been obtained and analyzed to yield four sets each of 24 dipolar couplings. These couplings were then used to investigate the structure of the ring and the ene fragments of the molecule, and the position of the maximum, [lowercase_phi_synonym]0, in the ring–ene bond rotational probability distribution. To do this, the effect on the dipolar couplings of small-amplitude vibrational motion was taken into account using vibrational wave functions calculated by molecular orbital and density functional methods. It is concluded that the NMR data are consistent with the ring fragment, averaged over the ring–ene rotation, planar, while the ene fragment is not. The value of [lowercase_phi_synonym]0 is found to be 18.0°±0.2° for the two solutions, compared with a value of 27° calculated by the molecular method MP2/6-31G*. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]