Theoretical studies of poly(para-phenylene vinylene) (PPV) and poly(para-phenylene) (PPP)

The electroluminescence from PPV and the blue light emission from PPP constitute exciting subjects of study. The band gap of these semiconducting polymers can be engineered in a wide range from red to ultraviolet by structural changes made on them. In the present work, we present a theoretical approach based on semiempirical and ab initio total energy and force calculations of PPV and PPP. We perform a conformational analysis in order to investigate the connection between their structural, optical and electronic properties. We use the large cell approach, in connection with the semiempirical quantum method Extended Hückel (BICON-CEDiT code) and the density functional theory (DFT) within the full-potential linearized augmented-plane-wave method (FPLAPW) as implemented in the computational code WIEN2k. Our results are compared to other calculations and to optical absorption measurements. q 2003 Elsevier Science Ltd. All rights reserved.