The charge mobility of molecular semiconductors is limited by the large fluctuation of intermolecular transfer integrals, often referred to as off-diagonal dynamic disorder, which causes transient localization of the carriers’ eigenstates. Using a recently developed theoretical framework, we show here that the electronic structure of the molecular crystals determines its sensitivity to intermolecular fluctuations. We build a map of the transient localization lengths of high-mobility molecular semiconductors to identify what patterns of nearest-neighbour transfer integrals in the two-dimensional (2D) high-mobility plane protect the semiconductor from the effect of dynamic disorder and yield larger mobility. Such a map helps rationalizing the transport properties of the whole family of molecular semiconductors and is also used to demonstrate why common textbook approaches fail in describing this important class of materials. These results can be used to rapidly screen many compounds and design new ones with optimal transport characteristics.

分子半导体的电荷迁移率受到分子间转移积分的大波动的限制，通常被称为对角动态紊乱，这会导致载流子本征态的瞬时定位。使用最近开发的理论框架，我们在这里显示了分子晶体的电子结构决定了其对分子间波动的敏感性。我们建立了高迁移率分子半导体的瞬态定位长度的图，以识别二维（2D）高迁移率平面中的最近邻居转移积分的哪些模式可以保护半导体免受动态无序的影响并产生更大的迁移率。这样的图谱有助于合理化整个分子半导体家族的传输性质，还用于说明为什么普通的教科书方法无法描述这种重要的材料类别。这些结果可用于快速筛选许多化合物并设计具有最佳转运特性的新化合物。