Yang Yanyan, Jin Qianqian, Yin Shiwei
Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an City 710119, People's Republic of China.
Phys Chem Chem Phys. 2024 Sep 11;26(35):22900-22911. doi: 10.1039/d4cp01568a.
For planar and rigid π-conjugated molecular systems, electrostatic and inductive interactions are pivotal in governing molecular packing structures and electron polarization energies. These electrostatic interactions typically exhibit an anisotropic nature within π-conjugated systems. In this study, we utilize the atoms in molecules (AIM) theory in conjunction with linear response theory to decompose molecular polarizability into distributed atomic polarizability tensors. On the basis of atomic polarizability tensors, we extended an anisotropic polarizable model into the AMOEBA polarizable force field. Both anisotropic and isotropic polarizable models in combination with various density functional theory (DFT)-derived atomic multipoles were applied to optimize the experimental crystals of naphthalene and anthracene. Furthermore, these two types of electrostatic models, coupled with the evolutionary algorithm USPEX program, are utilized to predict the crystal structures of oligoacenes. Our findings demonstrate that the anisotropic polarizable model exhibits superior performance in crystal refinement and crystal structure prediction. This enriched anisotropic polarizable model is seamlessly integrated into the AMOEBA polarizable force field and readily applicable within our modified Tinker program.
对于平面且刚性的π共轭分子体系，静电相互作用和诱导相互作用在决定分子堆积结构和电子极化能方面起着关键作用。这些静电相互作用在π共轭体系中通常表现出各向异性。在本研究中，我们将分子中的原子（AIM）理论与线性响应理论相结合，将分子极化率分解为分布的原子极化率张量。基于原子极化率张量，我们将一种各向异性极化模型扩展到AMOEBA极化力场。各向异性和各向同性极化模型与各种密度泛函理论（DFT）导出的原子多极矩相结合，用于优化萘和蒽的实验晶体。此外，这两种静电模型与进化算法USPEX程序相结合，用于预测寡并苯的晶体结构。我们的研究结果表明，各向异性极化模型在晶体精修和晶体结构预测方面表现出卓越的性能。这种丰富的各向异性极化模型无缝集成到AMOEBA极化力场中，并且可以在我们修改后的Tinker程序中轻松应用。
