Fast, Faithful Simulations of Donor-Acceptor Interface Morphology

The local structure of conjugated polymers governs key optoelectronic properties, such as charge conduction and photogeneration at donor-acceptor interfaces. Because conjugated polymers are large, stiff, and relax slowly, all-atom molecular dynamics simulations are computationally expensive. Here, we describe a coarse-graining method that exploits the stiffness of constituent aromatic moieties by representing each moiety as rigidly bonded clusters of atoms wherein virtual sites replace several atoms. This approach significantly reduces the degrees of freedom while faithfully representing the shape and interactions of the moieties, resulting in 10 times faster simulations than all-atom simulations. Simulation of a donor polymer (P3HT) and a non-fullerene acceptor (O-IDTBR) validates the coarse-graining method by comparing structural properties from experiments, such as the density and persistence length. The fast simulation produces equilibrated systems with realistic morphologies. The simulation results of an equimolar mixture of P3HT, with a molecular weight of 1332 g mol-1, and an O-IDTBR mixture suggest that the interface width must be larger than 7 nm. Also, we investigate the effect of slow cooling on morphologies, particularly the number of close contacts that facilitates carrier transport. Slow cooling increases close contacts, and the effect is more pronounced in crystal-forming P3HT than in O-IDTBR, where bulky side-groups hinder crystal formation.