Mechanoelectric Response of Single-Crystal Rubrene from Ab Initio Molecular Dynamics

[Image: see text] A robust understanding of the mechanoelectric response of organic semiconductors is crucial for the development of materials for flexible electronics. In particular, the prospect of using external mechanical strain to induce a controlled modulation in the charge mobility of the material is appealing. Here we develop an accurate computational protocol for the prediction of the mechanical strain dependence of charge mobility. Ab initio molecular dynamics simulations with a van der Waals density functional are carried out to quantify the off-diagonal electronic disorder in the system as a function of strain by the explicit calculation of the thermal distributions of electronic coupling matrix elements. The approach is applied to a representative molecular organic semiconductor, single-crystal rubrene. We find that charge mobility along the high-mobility direction a⃗ increases with compressive strain, as one might expect. However, the increase is larger when compressive strain is applied in the perpendicular direction than in the parallel direction with respect to a⃗, in agreement with experimental reports. We show that this seemingly counterintuitive result is a consequence of a significantly greater suppression of electronic coupling fluctuations in the range of 50–150 cm(–1), when strain is applied in the perpendicular direction. Thus our study highlights the importance of considering off-diagonal electron–phonon coupling in understanding the mechanoelectric response of organic semiconducting crystals. The computational approach developed here is well suited for the accurate prediction of strain–charge mobility relations and should provide a useful tool for the emerging field of molecular strain engineering.