Nuclear tunneling effects of charge transport in rubrene, tetracene, and pentacene

The mechanism of charge transport in organic materials is still controversial from both experimental and theoretical perspectives. At room temperature, molecular deformations interact strongly with the charge carrier both through intermolecular and intramolecular phonons, suggesting a thermally activated hopping mechanism as described by the Marcus electron transfer theory. However, several experimental measurements have indicated that the electronic transport behaves in a "bandlike" manner, as indicated by a decrease in mobility with increasing temperature, in contradiction to the Marcus description. Bandlike first-principles calculations based on the Holstein-Peierls model tend to overestimate the charge mobility by about 2 orders of magnitude. Here, a hopping model is derived that not only quantitatively describes the charge mobility but also explains the observed bandlike behavior. This model uses the quantum version of charge-transfer theory coupled with a random-walk simulation of charge diffusion. The results bridge the gap between the two extreme mechanisms. This first-principles method predicts the room-temperature hole mobilities to be 2.4, 2.0, and 0.67 cm(2)/V s, for rubrene, pentacene, and tetracene, respectively, in good agreement with experiment.