The intramolecular charge transfer properties of a phenyl-end-capped aniline tetramer (ANIH) and a chloro-substituted derivative (ANICl) as organic semiconductors were theoretically studied through the first-principles calculation based on the Marcus–Hush theory. The reorganization energies, intermolecular electronic couplings, angular resolution anisotropic mobilities, and density of states of the two crystals were evaluated. The calculated results demonstrate that both ANIH and ANICl crystals show the higher electron transfer mobilities than the hole-transfer mobilities, which means that the two crystals should prefer to function as n-type organic semiconductors. Furthermore, the angle dependence mobilities of the two crystals show remarkable anisotropic character. The maximum mobility μ_max of ANIH and ANICl crystals is 1.3893 and 0.0272 cm² V⁻¹ s⁻¹, which appear at the orientation angles near 176°/356° and 119°/299° of a conducting channel on the a-b reference plane. It is synthetically evaluated that the ANIH crystal possesses relatively lower reorganization energy, higher electronic coupling, and electron transfer mobility, which means that the ANIH crystal may be the more ideal candidate as a high performance n-type organic semiconductor material. The systematic theoretical studies on organic crystals should be conducive to evaluating the charge-transport properties and designing higher performance organic semiconductor materials.

中文翻译：

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作为共轭有机半导体的PANI的电荷转移迁移率和电导率

通过基于Marcus-Hush理论的第一性原理理论上研究了苯基端基苯胺四聚体（ANIH）和氯取代衍生物（ANICl）作为有机半导体的分子内电荷转移特性。评价了重组能量，分子间电子耦合，角分辨率各向异性迁移率和两种晶体的状态密度。计算结果表明，ANIH和ANICl晶体均显示出比空穴迁移率更高的电子迁移率，这意味着这两种晶体应优先用作n型有机半导体。此外，两种晶体的角度依赖性迁移率显示出显着的各向异性特征。最大的移动性μ_最大ANIH和ANICl晶体的晶体取向为1.3893和0.0272 cm ² V ^-1 s ^-1，它们出现在ab参考平面上导电通道的176°/ 356°和119°/ 299°附近的取向角上。综合评估表明，ANIH晶体具有相对较低的重组能，较高的电子耦合和电子转移迁移率，这意味着ANIH晶体可能是更理想的高性能n型有机半导体材料。对有机晶体的系统理论研究应有助于评估电荷传输性能和设计更高性能的有机半导体材料。