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The stiffness of a fully stretched polyethylene chain: A Raman jet spectroscopy extrapolation
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Linear alkanes with C-atoms are partially relaxed into their stretched all-transconformation by supersonic jet expansion. Their longitudinal acoustic modes are identified by spontaneous Raman scattering and deperturbed from transverse bending mode components and Fermi resonance with combination states of the same symmetry. Comparison with quantum chemical predictions of the longitudinal modes in hydrocarbon chains with up to 54 C-atoms allows for a reliable extrapolation to the limiting product for large , from which the elastic modulus of an ideal polyethylene chain in vacuum may be estimated at . Differences to solid state determinations of this quantity are discussed.
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