Liquid crystal properties of the n-alkyl-cyanobiphenyl series from atomistic simulations with Ab initio derived force fields

Lengthy molecular dynamics (MD) simulations were performed at constant atmospheric pressure and different temperatures for the series of the 4-n-alkyl-4'-cyanobiphenyls (nCB) with n = 6, 7, and 8. The accurate atomistic force field (Bizzarri, M.; Cacelli, I.; Prampolini, G; Tani, A. J. Phys. Chem. A 2004, 108, 10336), successfully employed to reproduce thermodynamic and transport properties of the 5CB molecule, has here been extended to higher homologues. Nematic and isotropic phases were found for all members of the series, and also, a smectic phase was (tentatively) identified for 8CB at 1 atm and 300 K. Transition temperatures reproduce the experimental values within +/- 10 K. Also, structural properties as second and fourth rank orientational order parameters are in good agreement with the corresponding experimental quantities. This means that the well-known odd-even effect, observed for many properties along the nCB series, is well reproduced, despite the narrow range of oscillations, e.g., in clearing temperatures. A detailed analysis of the correlation between molecular properties and odd-even effects is presented.