Center for Nano and Molecular Science and Technology, The University of Texas at Austin, Austin, Texas 78712, USA.
Phys Rev Lett. 2011 Jun 3;106(22):226403. doi: 10.1103/PhysRevLett.106.226403. Epub 2011 Jun 2.
We use first-principles computational methods to examine hole trapping in organic molecular crystals. We present a computational scheme based on the tuning of the fraction of exact exchange in hybrid density functional theory to eliminate the many-electron self-interaction error. With small organic molecules, we show that this scheme gives accurate descriptions of ionization and dimer dissociation. We demonstrate that the excess hole in perfect molecular crystals forms self-trapped molecular polarons. The predicted absolute ionization potentials of both localized and delocalized holes are consistent with experimental values.
我们使用第一性原理计算方法研究了有机分子晶体中的空穴俘获。我们提出了一种基于混合密度泛函理论中精确交换分数调节的计算方案，以消除多电子自相互作用误差。对于小分子，我们表明该方案可以准确描述电离和二聚体解离。我们证明了完美分子晶体中的多余空穴会形成自陷分子极化子。预测的局域和离域空穴的绝对电离势与实验值一致。
