Ab initio finite oligomer method for nonlinear optical properties of conjugated polymers. Hartree–Fock static longitudinal hyperpolarizability of polyacetylene

Abstract

Ab initio restricted Hartree–Fock 6‐31G calculations are reported for the static longitudinal hyperpolarizability of the linear polyenes C₄H₆ through C₄₄H₄₆. Using a new extrapolation technique the infinite chain value in polyacetylene is determined with an accuracy similar to that achieved for small molecules. This is the first in a series of articles leading to a comprehensive ab initio treatment for the nonlinear optical properties of conjugated polymers.