Chain length dependence of static longitudinal polarizabilities and hyperpolarizabilities in linear polyynes

Abstract

Ab initio calculations of the static longitudinal dipole polarizability αL and second dipole hyperpolarizability γL are reported for the linear C2nH2 polyynes up to C44H2 . Basis set requirements diminish with increasing chain length. The intermediate neglect of differential overlap (INDO) method is able to mimic the ab initio results if the Ohno–Klopman parameterization is used. The values per acetylenic linkage, αL/n and γL/n, converge very slowly with chain length; they are extrapolated to the infinite chain limit.