Stretching and folding of 2-nanometer hydrocarbon rods

Abstract

Linear alkanes C_nH_2n+2 in vacuum isolation are finite models for an infinite polyethylene chain. Using spontaneous Raman scattering in supersonic jet expansions for n = 13–21 in different spectral ranges, we determine the minimal chain length n_h for the cohesion-driven folding of the preferred extended all-trans conformation into a hairpin structure. We treat fully stretched all-trans alkanes as molecular “nanorods” and derive Young's modulus E for the stretching of an isolated single-strand polyethylene fibre by extrapolating the longitudinal acoustic mode to infinite chain length. Two key quality parameters for accurate intra- and intermolecular force fields of hydrocarbons (n_h = 18 ± 1, E = 305 ± 5 GPa) are thus derived with high accuracy from experimental spectroscopy.