Theory of electronic states and excitations in PPV

We present a consistent theoritical picture for optical properties of phenyl based polymers, especially for the PPV family. The model is based upon an analytical solution for the band structure of PPV oligomers, while invoking the dominant Coulomb corrections for electron-hole interactions. The adjustable parameters are only the common shift for the bands centers of gravity and a dielectric susceptibility at small distances. Our picture gives a clear understanding for the origin of all possible transitions in linear and nonlinear optics. We describe both tightly bound localized excitons and excitons of intermediate range (i.e. of both the Frenkel and Wannier-Mott types). The quantitative description of excitons is obtained from the long range Coulomb interactions. We emphasize where the ring torsion plays a role in the overall energy minimization of the excited state. This article provides theory details for the joint article [S. Brazovskii, N. Kirova, A.R. Bishop, V. Klimov, D. McBranch, N. N. Barashkov, J.P. Ferraris, Opt. Mater. 9 (1998) 472], where a complete picture was outlined. (C) 1998 Elsevier Science B.V.