Charge carrier transport in organic semiconductors is at the heart of many revolutionary technologies ranging from organic transistors, light-emitting diodes, flexible displays and photovoltaic cells. Yet, the nature of charge carriers and their transport mechanism in these materials is still unclear. Here we show that by solving the time-dependent electronic Schrödinger equation coupled to nuclear motion for eight organic molecular crystals, the excess charge carrier forms a polaron delocalized over up to 10–20 molecules in the most conductive crystals. The polaron propagates through the crystal by diffusive jumps over several lattice spacings at a time during which it expands more than twice its size. Computed values for polaron size and charge mobility are in excellent agreement with experimental estimates and correlate very well with the recently proposed transient localization theory.

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.

We have recently introduced an efficient semi-empirical non-adiabatic molecular dynamics method for the simulation of charge transfer/transport in molecules and molecular materials, denoted fragment orbital-based surface hopping (FOB-SH) [J. Spencer et al., J. Chem. Phys. 145, 064102 (2016)]. In this method, the charge carrier wavefunction is expanded in a set of charge localized, diabatic electronic states and propagated in the time-dependent potential due to classical nuclear motion. Here we derive and implement an exact expression for the non-adiabatic coupling vectors between the adiabatic electronic states in terms of nuclear gradients of the diabatic electronic states. With the non-adiabatic coupling vectors (NACVs) available, we investigate how different flavours of fewest switches surface hopping affect detailed balance, internal consistency, and total energy conservation for electron hole transfer in a molecular dimer with two electronic states. We find that FOB-SH satisfies detailed balance across a wide range of diabatic electronic coupling strengths provided that the velocities are adjusted along the direction of the NACV to satisfy total energy conservation upon a surface hop. This criterion produces the right fraction of energy-forbidden (frustrated) hops, which is essential for correct population of excited states, especially when diabatic couplings are on the order of the thermal energy or larger, as in organic semiconductors and DNA. Furthermore, we find that FOB-SH is internally consistent, that is, the electronic surface population matches the average quantum amplitudes, but only in the limit of small diabatic couplings. For large diabatic couplings, inconsistencies are observed as the decrease in excited state population due to frustrated hops is not matched by a corresponding decrease in quantum amplitudes. The derivation provided here for the NACV should be generally applicable to any electronic structure approach where the electronic Hamiltonian is constructed in a diabatic electronic state basis.