Departamento de Química Física, University of Alicante, E-03080 Alicante, Spain.
Phys Chem Chem Phys. 2010 Aug 28;12(32):9381-8. doi: 10.1039/b925652k. Epub 2010 Jul 7.
The generation of mobile charges and their transport across organic layers are commonly the most critical steps affecting the performance of organic-based electronic devices. Charge-transport properties are often described by quantum-chemical calculations which, however, face a challenge when the nanostructure of the material has to be concomitantly addressed together with electronic aspects. We tackle here this challenging task by applying dispersion-corrected Density Functional Theory methods, which allow us not only to give an insight into the molecular packing but also to accurately extract key molecular parameters governing charge transport. When applied to a set of functionalized (chlorinated) tetracene molecules, our approach yields the expected molecular packing, which has motivated its use to predict the packing of other fluorinated or brominated derivatives which are not yet synthesized. The charge mobilities have been calculated on the basis of the determined packing motifs and exhibit significant differences among the derivatives. This work paves the way towards the development of a computational protocol that could be implemented not only for idealized packing motifs or known crystallographic structures but also for self-organizing materials as well as supramolecular and host-guest interactions.
在有机层中产生并传输移动电荷通常是影响基于有机的电子设备性能的最关键步骤。电荷输运性质通常通过量子化学计算来描述，但当必须同时解决材料的纳米结构和电子方面的问题时，这就面临着挑战。我们通过应用色散校正的密度泛函理论方法来解决这个具有挑战性的任务，该方法不仅使我们能够深入了解分子堆积，还能够准确提取控制电荷输运的关键分子参数。当将该方法应用于一组功能化（氯化）并四苯分子时，我们的方法得到了预期的分子堆积，这激发了我们将其用于预测其他尚未合成的氟化或溴化衍生物的堆积。基于确定的堆积模式计算了电荷迁移率，并表现出衍生物之间的显著差异。这项工作为开发一种计算协议铺平了道路，该协议不仅可以用于理想化的堆积模式或已知的晶体结构，还可以用于自组织材料以及超分子和主客体相互作用。
