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NMR of Short-Chain Hydrocarbons in Nematic and Smectic A Liquid Crystals

TitleNMR of Short-Chain Hydrocarbons in Nematic and Smectic A Liquid Crystals
Publication TypeJournal Article
Year of Publication2013
AuthorsWeber, ACJ, Dong, RY, W. Meerts, L, Yang, X, E. Burnell, E
JournalJOURNAL OF PHYSICAL CHEMISTRY A
Volume117
Pagination9224-9234
Date PublishedSEP 26
ISSN1089-5639
Abstract

The proton NMR spectra of ethane, propane, and n-butane codissolved and orientationally ordered in two liquid crystal solvents that exhibit both nematic (N) and smectic A (SmA) phases (one of which also has a reentrant nematic (RN) phase) are analyzed using CMA-ES (covariance-matrix adaptation evolution strategy). To deal with. problems arising from the broad liquid crystal background signal, a smoothed experimental spectrum is fitted to a smoothed calculated spectrum. The ethane and propane dipolar couplings and anisotropic energy parameters scale with each other, and the n-butane couplings are assumed to behave likewise. This restriction on the relative values of the n-butane energy parameters facilitates a fit to the temperature dependence of the n-butane dipolar couplings, in which the six n-butane energy parameters (three for trans and three for gauche), the isotropic trans-gauche energy difference E-tg, and its temperature coefficient E'(tg), and the methyl CCH angle decrease are obtained. Unlike earlier studies, the fit does not employ a model for the anisotropic intermolecular potential. The nematic potential in the SmA phase of the liquid crystal mixture 6OCB/8OCB is estimated by interpolated values obtained from the ethane spectra for the N and RN regions. Analysis of results for the SmA phase involves adding a nematic-smectic coupling prefactor and a smectic prefactor. Spectra obtained in the liquid crystal 8OCB are calculated with no adjustable parameters, scaling the potentials using the ethane values, and the agreement between experiment and calculation is outstanding. Conformer populations are affected by the environment, and the isotropic solute-solvent interactions result in increased gauche populations, whereas anisotropic interactions increase the trans probability. The trans probability in the SmA phase is slightly lower than expected from the nematic results.

DOI10.1021/jp404315t