Non-Local Density Functional Description of Poly-Para-Phenylene Vinylene

A fully non-local exchange-correlation formalism within the framework of density functional theory, known as the weighted density approximation (WDA), has been applied to the conjugated polymer poly-para-phenylene vinylene (PPV) and is shown to lead to a marked improvement in the agreement of theory and experiment for the electronic band structure of the conjugated polymer. In particular, some new model WDA functions are developed, which substantially increase the electronic band gap of the polymer relative to those obtained with the local density approximation and generalized gradient approximation. The calculated band gap of PPV is quantitatively or at least semiquantitatively in agreement with the experimental data.