Crystal structure versus charge transport in organic single crystals of [1]benzothieno[3,2-b][1]benzothiophene derivatives from a multiscale theoretical study

[1]Benzothieno[3,2-b][1]benzothiophene derivatives with high air stability have recently displayed excellent charge transport properties in field-effect devices. In particular, the average charge mobilities can reach as high as 16.4 ± 6.1 cm² V^-1 s^-1 in devices with a high quality semiconductor/insulator interface, which is comparable to the performance for a rubrene single-crystal device. To better understand these excellent charge transport properties, a multiscale approach combining molecular dynamics and quantum-chemical calculations was used in this work to assess the structure-property relationship for three of the [1]benzothieno[3,2-b][1] benzothiophene derivatives with different alkyl side chains. It is indicated that the extremely large electronic couplings along the a-axis direction are responsible for the excellent charge transport properties in these systems. While the molecular packings are centrosymmetrical in the ab plane, the lattice vibrations were found to hamper the charge transport in optimized crystal structures at the COMPASS molecular mechanics level which is opposite to the recent findings that the lattice dynamics should have a negligible effect on the charge mobility in the centrosymmetrical plane. The reason for such behavior was analyzed and the predicted order of the overall charge mobilities for the studied systems was consistent with the experiments. Meanwhile, how well the force field reproduces the observed crystal structures and dimer intermolecular separations and orientations is discussed in this work. In addition, it is shown that the present charge transport model can not only predict the magnitude of the charge mobility but also the measured "band-like" charge transport in experiments, so the nuclear tunneling effect is very important for charge transport in organic semiconductors as was demonstrated in recent theoretical work.