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A model-free temperature-dependent conformational study of n-pentane in nematic liquid crystals

TitleA model-free temperature-dependent conformational study of n-pentane in nematic liquid crystals
Publication TypeJournal Article
Year of Publication2015
AuthorsE. Burnell, E, Weber, ACJ, Dong, RY, W. Meerts, L, de Lange, CA
JournalJOURNAL OF CHEMICAL PHYSICS
Volume142
Pagination024904
Date PublishedJAN 14
ISSN0021-9606
Abstract

The proton NMR spectra of n-pentane orientationally ordered in two nematic liquid-crystal solvents are studied over a wide temperature range and analysed using covariance matrix adaptation evolutionary strategy. Since alkanes possess small electrostatic moments, their anisotropic intermolecular interactions are dominated by short-range size-and-shape effects. As we assumed for n-butane, the anisotropic energy parameters of each n-pentane conformer are taken to be proportional to those of ethane and propane, independent of temperature. The observed temperature dependence of the n-pentane dipolar couplings allows a model-free separation between conformer degrees of order and conformer probabilities, which cannot be achieved at a single temperature. In this way for n-pentane 13 anisotropic energy parameters (two for trans trans, tt, five for trans gauche, tg, and three for each of gauche(+) gauche(+), pp, and gauche(+) gauche(-), pm), the isotropic trans-gauche energy difference E-tg and its temperature coefficient E-tg' tg are obtained. The value obtained for the extra energy associated with the proximity of the two methyl groups in the gauche(+) gauche(-) conformers (the pentane effect) is sensitive to minute details of other assumptions and is thus fixed in the calculations. Conformer populations are affected by the environment. In particular, anisotropic interactions increase the trans probability in the ordered phase. (C) 2015 AIP Publishing LLC.

DOI10.1063/1.4904822