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

The emergence of polymeric materials displaying high charge-carrier mobility values despite poor interchain structural order has spawned a renewal of interest in 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 intrachain charge transport simulations obtained by applying a robust surface hopping algorithm to a phenomenological Hamiltonian parametrized 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 intrachain charge-carrier mobility values in excess of 100 cm²/(V s) can be achieved through a proper chemical engineering of the backbones.