Long-Range Interactions Boost Singlet Exciton Diffusion in Nanofibers of π-Extended Polymer Chains

Raising the distance covered by singlet excitons during their lifetimes to values maximizing light absorption (a few hundred nm) would solve the exciton diffusion bottleneck issue and lift the constraint for fine (μ10 nm) phase segregation in bulk heterojunction organic solar cells. In that context, the recent report of highly ordered conjugated polymer nanofibers featuring singlet exciton diffusion length, LD, in excess of 300 nm is both appealing and intriguing [ Jin, X.; et al. Science 2018, 360 (6391), 897-900 ]. Here, on the basis of nonadiabatic molecular dynamics simulations, we demonstrate that singlet exciton diffusion in poly(3-hexylthiophene) (P3HT) fibers is highly sensitive to the interplay between delocalization along the polymer chains and long-range interactions along the stacks. Remarkably, the diffusion coefficient is predicted to rocket by 3 orders of magnitude when going beyond nearest-neighbor intermolecular interactions in fibers of extended (30-mer) polymer chains and to be resilient to interchain energetic and positional disorders.