title: Nuclear magnetic resonance study of alkane conformational statistics.
abstract: NMR spectra of ethane, propane, and n-butane as solutes in the nematic liquid crystals 4-n-pentyl-4(')-cyanobiphenyl (5CB) and Merck ZLI 1132 (1132) are investigated over a wide temperature range. The ratios of dipolar couplings of ethane to propane are constant over the entire temperature range. Assuming that this constancy applies to the butane conformers facilitates the separation of probability from order parameter. This separation allows the investigation of conformational distribution without the need of invoking any model for the anisotropic intermolecular potential. The results give an order matrix that is consistent with that predicted from model potentials that describe the orientational potential in terms of short-range size and shape effects. The isotropic intermolecular potential contribution to the trans-gauche energy difference E(tg) is found to be temperature dependent with the values and variation in agreement with that found when the same results are analyzed using the chord model for anisotropic interactions [A. C. J. Weber and E. E. Burnell, Chem. Phys. Lett. 506, 196 (2011)]. The fit obtained for 9 spectra in 5CB (63 dipolar couplings) has an RMS difference between experimental and calculated dipolar couplings of 2.7 Hz, while that for the 16 spectra in 1132 (112 couplings) is 6.2 Hz; this excellent fit with nine adjustable parameters suggests that the assumption of equal temperature dependencies of the order parameters for ethane, propane, and each conformer of butane is correct. Also the fit parameters (E(tg) and the methyl angle increase) obtained for 1132 and 5CB agree. The results indicate that the chord model, which was designed to treat hydrocarbon chains, is indeed the model of choice for these chains. The temperature variation of E(tg) provides a challenge for theoreticians. Finally, even better fits to the experimental dipolar couplings are obtained when the energy in the Boltzmann factor is used for scaling ethane to butane results. However, in this case the values obtained for E(tg) differ between 1132 and 5CB.
authors.affiliation: Chemistry Department, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada. elliott.burnell@ubc.ca
authors.forename: E Elliott
authors.initials: EE
authors.lastname: Burnell
authors.forename: Adrian C J
authors.initials: AC
authors.lastname: Weber
authors.forename: Cornelis A
authors.initials: CA
authors.lastname: de Lange
authors.forename: W Leo
authors.initials: WL
authors.lastname: Meerts
authors.forename: Ronald Y
authors.initials: RY
authors.lastname: Dong
mesh_terms: D000465:Algorithms; D000473:Alkanes / Q000737:chemistry*; D016880:Anisotropy; D002073:Butanes / Q000737:chemistry; D004980:Ethane / Q000737:chemistry; D050866:Liquid Crystals / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D011336:Probability; D011407:Propane / Q000737:chemistry; D012996:Solutions / Q000737:chemistry; D013696:Temperature
chemical_list: D000473:Alkanes; D002073:Butanes; D012996:Solutions; C046888:butane; D004980:Ethane; D011407:Propane