The Source of Helicity in Perfluorinated N-Alkanes

Abstract

The well-known helical conformations of double stranded DNA and poly(alanine) are stabilized by inter- and intramolecular hydrogen bonds, respectively. Perfluorinated n-alkanes also exhibit stable helical conformations, with ordered chiralities at low temperatures. In the absence of hydrogen bonds, one may ask what forces stabilize perfluorinated n-alkane helices. We combine ab initio and empirical data to study the likely classical source of this helical behavior. Past studies point to bad sterics (van der Waals interactions) between neighboring fluorine atoms as the source of helicity in perfluorinated linear alkanes. In these early studies electrostatics were ignored. We undertook a detailed force field parameter optimization strategy, using experimental and ab initio data, to obtain transferable, uncorrelated estimates of the separate classical energy components. We find that the dominant energy term, the source of helicity, is electrostatics. The coulomb repulsion, from a classical fixed-charge model, reproduces reasonably well the position of the energy minima and the energy barrier between the helical and the all-trans conformations. Polarization effects, changes in atomic charges as a result of conformational changes, are not significant. Dihedral interactions and van der Waals terms adjust the exact position of the minima only slightly. In the absence of electrostatic contributions, van der Waals and dihedral interactions predict the incorrect stable conformations.