Abstract
For conformational analysis of chain molecules incorporated in nematic fields, a rotational isomeric state (RIS) scheme was revised for use with the maximum entropy method. Analysis thus based proceeds as follows. 1) All possible conformations are enumerated within the RIS approximation. 2) The principal Axes of inertia, determined for each conformer, are considered molecular axes, and orientational order parameters are evaluated from dimensions of a rectangular parallelepiped closely fitted to the conformer. 3) Conformational statistical weight factors of first- and second-order interactions are adjusted and order parameters are scaled so as to reproduce experimental observation and maximize the information entropy regarding conformer populations. By this method, 1H-1H dipolar couplings observed from n-hexane, n-heptane, n-octane, n-nonane, and n-decane dissolved in a nematic liquid crystal Kodak EK11650 p-pentylphenyl-2-chloro(4-benzylbenzoyloxy)-benzoate [M.E. Rosen, S.P. Rucker, C. Schmidt, and A. Pines, J. Phys. Chem. 97, 3858 (1993)] were analyzed. For all n-alkanes, good agreement between theory and experiment was attained. Anisotropic conformers were slightly more populated than in the free state. The present results were quantitatively comparable to those of analysis using the mean-field theory.
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Sasanuma, Y. Conformational Analysis of Chain Molecules in Liquid Crystalline Phases by a Rotational Isomeric State Scheme with Maximum Entropy Method I. 1H-1H Dipolar Couplings from n-Alkanes Dissolved in a Nematic Solvent. Polym J 32, 883–889 (2000). https://doi.org/10.1295/polymj.32.883
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DOI: https://doi.org/10.1295/polymj.32.883
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