화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.120, No.9, 2507-2516, 2016
Polymer Optical Constants from Long-Range Corrected DFT Calculations
A methodology to calculate refractive indices of plastics based on the Lorentz-Lorenz equation has been proposed. The polarizability of the nonconjugated polymer repeat units is predicted using the long-range corrected functionals. The end effect corrections in repeat unit models are essential to achieve accuracy similar to that observed for molecular liquids (ca. 1% in mean absolute deviation). The functionals with 100% Hartree-Fock (HF) exchange in the long-range limit perform best for aromatic and other hydrogen-deficient compounds; the Coulomb-attenuated hybrid exchange-correlation functional (CAM-B3LYP) performs very well for hydrogen-rich (usually, fully saturated) compounds. Exceptionally good agreement is observed for the sets of wavelength-dependent refractive index data for polystyrene, poly(methyl methacrylate), and for poly(perfluoro-4-vinyloxy-l-butene) (CYTOP), for which the root-mean-square deviations are 0.004, 0.002, and 0.004, respectively.