Molecular stacking motifs in solid play a pivotal role on the charge transport properties of materials. The relationship between molecular structure and packing motifs in solid remains challenging. In the present work, the single crystal structures of PEN-O, PEN-N, PEN-CF₃ and TPDO were predicted by evolutionary algorithm using the USPEX program. The stacking motifs, the electronic structures and the stabilities of pentacene (PEN) derivatives are systematically investigated by employing density functional theory. Our study expounded how the introduction of heteroatoms (oxygen-atom and nitrogen-atom) and substituent (trifluoromethyl) adjust their electronic structure effectively to improve the capability of carrier injection. Hirshfeld surface analysis was performed for the intermolecular close contact points to rationalize the molecular stacking patterns in solid. In addition, electrostatic potential and energy decomposition by symmetry adapted perturbation theory are analyzed to reveal the effects of heteroatoms and substituents on charge distribution and noncovalent interactions. Through introducing heteroatoms and substituents into PEN, the charge redistribution leads to non-uniform electrostatic potentials of conjugated molecular skeleton, which results in the change of the stacking patterns from herringbone to π-stacking. Furthermore, incorporating oxygen-atom or nitrogen-atom into PEN decreases dispersion energies, while modifying PEN with trifluoromethyl increases the dispersion energy. However, both of them lead to the decrease of the electrostatic and exchange-repulsion energy.

固体中的分子堆积基序对材料的电荷传输性质起着关键作用。固体中的分子结构和堆积图案之间的关系仍然具有挑战性。在目前的工作中，使用USPEX程序通过进化算法预测了PEN-O，PEN-N，PEN-CF ₃和TPDO的单晶结构。并五苯的堆积图案，电子结构和稳定性（PEN通过使用密度泛函理论对导数进行系统地研究。我们的研究阐述了杂原子（氧原子和氮原子）和取代基（三氟甲基）的引入如何有效地调节其电子结构，以提高载流子注入的能力。对分子间的紧密接触点进行了Hirshfeld表面分析，以合理化固体中的分子堆积模式。此外，通过对称适应微扰理论对静电势和能量分解进行了分析，以揭示杂原子和取代基对电荷分布和非共价相互作用的影响。通过将杂原子和取代基引入PEN，电荷的重新分布导致共轭分子骨架的静电势不均匀，从而导致堆叠模式从人字形变为π堆叠。此外，将氧原子或氮原子结合到PEN中会降低分散能，而用三氟甲基改性PEN会增加分散能。但是，它们都导致静电和交换排斥能的降低。