Theoretical characterization of the electronic properties of extended thienylenevinylene oligomers

We present semi-empirical 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 ∼30◦ angle. We show that these oligomers possess extensive π-electron delocalization along the molecular backbone which makes them interesting for future electronic applications such as molecular wires.