Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol.256, 711-719, 1994
Delocalization Contributions to Polyacetylene Force-Fields
The force fields of trans and cis-polyacetylene(PA) are obtained in internal coordinates by combining linear-response analysis of the Raman and ir shifts due to pi-electrons, molecular force-field methods, and the Huckel susceptibility of k not equal O phonons. We find transferable electron-phonon coupling constants, exponential transfer integrals t(R), and coupling to CCC bends through the Coulomb potential V(R). The electronic response of cis-PA is 56% of the trans susceptibility, indicative of reduced delocalization and an energy gap in the A(g) manifold due to third-neighbor V(R) terms.