Theoretical characterization of the electronic properties of extended thienylenevinylene oligomers

We present semiempirical tight binding calculations on thienylenevinylene oligomers up to the hexadecamer stage (n=16) and ab initio calculations based on the local density approximation up to n=8. The results correctly describe the experimental variations of the gap versus size, the optical spectra, and the electrochemical redox potentials. We propose a simple model to deduce from the band structure of the polymer chain the electronic states of the oligomers close to the gap. We analyze the evolution of the gap as a function of the torsion angle between consecutive cells: the modifications are found to be small up to a similar to 30 degrees angle. We show that these oligomers possess extensive pi-electron delocalization along the molecular backbone which makes them interesting for future electronic applications such as molecular wires. (C) 1999 American Institute of Physics. [S0021-9606(99)31937-1].