Crystalline Moduli of Polymers, Evaluated from Density Functional Theory Calculations under Periodic Boundary Conditions.

A theoretical methodology based on quantum chemistry to calculate mechanical properties of polymer crystals has been developed and applied to representative polymers. By density functional theory calculations including a dispersion force correction under three-dimensional periodic boundary conditions, crystal structures of poly(methylene oxide) (PMO), polyethylene (PE), poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), and poly(butylene terephthalate) (PBT) were optimized and their mechanical properties, such as crystalline moduli and linear and volume compressibilities, were calculated. The optimized crystal structures were proved to be fully consistent with those determined by X-ray and neutron diffraction. The crystalline moduli (E ∥) parallel to the chain axis were calculated to be 114 GPa (PMO), 333 GPa (PE), 182 GPa (PET), 7.1 GPa (PTT), and 20.8 GPa (PBT) and compared with those determined from X-ray diffraction, Raman spectroscopy, and neutron inelastic scattering experiments. Herein, the E ∥ values thus determined are interpreted in terms of conformational characteristics of the polymeric chains and the validity of the homogeneous stress hypothesis adopted in the X-ray diffraction method is also discussed.