Statistical model for intermolecular adhesion in π-conjugated polymers

We propose an interchain binding mechanism in pi-conjugated polymers based on the intermolecular tunneling of the delocalized electrons occurring at points where the polymers cross. This mechanism predicts specific bound structures of chains that depend on whether they are semiconducting or metallic. Semiconducting chains should form polyacenelike states exhibiting binding at every other site, while (doped) metallic chains can bind at each site. We also show that solitons colocalize with the intermolecular binding sites thereby strengthening the binding effect and investigate the conformational statistics of the resulting bimolecular aggregates.