Crossover from Hopping to Band-Like Charge Transport in an Organic Semiconductor Model: Atomistic Nonadiabatic Molecular Dynamics Simulation

[Image: see text] The mechanism of charge transport (CT) in a 1D atomistic model of an organic semiconductor is investigated using surface hopping nonadiabatic molecular dynamics. The simulations benefit from a newly implemented state tracking algorithm that accounts for trivial surface crossings and from a projection algorithm that removes decoherence correction-induced artificial long-range charge transfer. The CT mechanism changes from slow hopping of a fully localized charge to fast diffusion of a polaron delocalized over several molecules as electronic coupling between the molecules exceeds the critical threshold V ≥ λ/2 (λ is the reorganization energy). With increasing temperature, the polaron becomes more localized and the mobility exhibits a “band-like” power law decay due to increased site energy and electronic coupling fluctuations (local and nonlocal electron–phonon coupling). Thus, reducing both types of electron–phonon coupling while retaining high mean electronic couplings should be part of the strategy toward discovery of new organics with high room-temperature mobilities.