Design Rules to Maximize Charge-Carrier Mobility along Conjugated Polymer Chains.

The emergence of polymeric materials displaying high charge-carrier mobility values despite poor inter-chain structural order has spawned a regain of interest for the identification of structure-property relationships pertaining to the transport of charges along conjugated polymer chains and the subsequent design of optimized architectures. Here, we present the results of intra-chain charge transport simulations obtained by applying a robust surface hopping algorithm to a phenomenological Hamiltonian parameterized against first-principles simulations. Conformational effects are shown to provide a clear signature in the temperature dependent charge-carrier mobility that complies with recent experimental observations. We further contrast against molecular crystals the evolution with electronic bandwidth and electron-phonon interactions of the room-temperature mobility in polymers, showing that intra-chain charge-carrier mobility values in excess of 100 cm2/Vs can be achieved through a proper chemical engineering of the backbones.