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Molecules with large-amplitude torsional motion partially oriented in a nematic liquid crystal: Ethane and isotopomers

TitleMolecules with large-amplitude torsional motion partially oriented in a nematic liquid crystal: Ethane and isotopomers
Publication TypeJournal Article
Year of Publication2005
AuthorsBurnell, EE, de Lange, CA, Barnhoorn, JBS, Aben, I, Levelt, PF
JournalJournal of Physical Chemistry A
Volume109
Pagination11027-11036
Date PublishedDec
Type of ArticleArticle
ISBN Number1089-5639
KeywordsANISOTROPIC, ELECTRIC-FIELD GRADIENTS, ENVIRONMENTS, FORCE-FIELDS, H-2 NMR, NUCLEAR-MAGNETIC-RESONANCE, orientational order, POLYATOMIC-MOLECULES, ROTATION, SPECTRA, VIBRATIONS
Abstract

An NMR study on ethane and five isotopomers dissolved in the nematic liquid crystal Merck ZLI 1132 is performed. A consistent set of dipolar and quadrupolar couplings is obtained. The dipolar couplings are corrected for harmonic vibrational effects, while the contribution from the torsional motion is incorporated classically. The corrected dipolar couplings cannot be understood in terms of a reasonable molecular structure unless effects of the reorientation-vibration interaction are taken into account. Assuming that the reorientation-vibration contributions that are known for the methyl group in methyl fluoride are transferable to ethane, excellent agreement between observed and calculated dipolar couplings is obtained on the basis of the ethane gas-phase structure. The observed and calculated deuterium quadrupolar couplings show discrepancies supporting the notion that average electric field gradients are important in liquid-crystal solvents. An important consequence of the transferability of the reorientation-vibration correlation is that in other molecules with a methyl group the same procedure as for ethane can be followed. Inclusion of this effect generally removes the need to interpret changes in observed dipolar couplings in terms of elusive chemical effects.

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