State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, People's Republic of China.
J Phys Chem A. 2012 Nov 26;116(46):11075-82. doi: 10.1021/jp3023474. Epub 2012 Apr 12.
The electron mobilities of two n-type pentacenequinone derivative organic semiconductors, 5,7,12,14-tetraaza-6,13-pentacenequinone (TAPQ5) and 1,4,8,11-tetraaza-6,13-pentacenequinone (TAPQ7), are investigated with use of the methods of electronic structure and quantum dynamics. The electronic structure calculations reveal that the two key parameters for the control of electron transfer, reorganization energy and electronic coupling, are similar for these two isomerization systems, and the charge carriers essentially display one-dimensional transport properties. The mobilities are then calculated by using the time-dependent wavepacket diffusion approach in which the dynamic fluctuations of the electronic couplings are incorporated via their correlation functions obtained from molecular dynamics simulations. The predicted mobility of TAPQ7 crystal is about six times larger than that of TAPQ5 crystal. Most interestingly, Fermi's golden rule predicts the mobilities very close to those from the time-dependent wavepacket diffusion method, even though the electronic couplings are explicitly large enough to make the perturbation theory invalid. The possible reason is analyzed from the dynamic fluctuations.
两种 n 型并五苯醌衍生物有机半导体，5,7,12,14-四氮-6,13-并五苯醌（TAPQ5）和 1,4,8,11-四氮-6,13-并五苯醌（TAPQ7）的电子迁移率，使用电子结构和量子动力学的方法进行了研究。电子结构计算表明，对于这两个异构化体系，控制电子转移的两个关键参数，重组能和电子耦合，是相似的，载流子基本上表现出一维输运性质。然后，通过使用含时波包扩散方法计算迁移率，其中通过从分子动力学模拟获得的相关函数来包含电子耦合的动态波动。预测的 TAPQ7 晶体的迁移率大约是 TAPQ5 晶体的六倍。最有趣的是，即使电子耦合大到使得微扰理论无效，费米黄金定则也能预测出非常接近含时波包扩散方法的迁移率。可能的原因从动态波动进行了分析。
