The electrostatic polarization plays an important role in determining the energy levels of charge carriers in organic solids, which is controlled by the atomic polarizability in AMOEBA polarizable force field. QTAIM-based space partitioning of molecular polarizability is utilized to uniformly parametrize the state-specific atomic polarizability (SSAP) of π-conjugated organic small molecules to avoid fitting molecular polarizability of some artificial training set. Herein, the SSAPs are applied to explicitly extrapolate the electrostatic polarization energy (E^pol) of the charge carriers of nine π-conjugated organic crystals including six p-type transfer materials, oligoacenes and TIPS-substituted oligoacenes, and three n-type transfer materials, F-substituted oligoacenes and TCNQ. Our results demonstrate that the electrostatic polarization energies of the hole carrier (E₊^pol) are smaller than that of the electron carrier (E_–^pol) for p-type molecules while E₊^pol are larger than E_–^pol for n-type molecules. SSAP-based E^pol values of oligoacenes behave as a nearly unvaried feature with the increase of conjugation length which is similar to implicit polarizable continuum model (PCM) results, while E^pol obtained from the default atomic polarizability behaves with a notable decrease. Implicit PCM can correctly capture most of electrostatic polarization of ions in bulk system although it slightly underestimates the gap between the electrostatic polarization of hole and electron carriers in oligoacene crystals. Our results demonstrate that this unified parametrized SSAP provides a reliable and cheap tool to estimate the energy landscape of charge carriers in condensed-phase organic solids.

中文翻译：

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有机分子晶体中载流子的静电极化能：与基于特定状态的原子极化率基于AMOEBA力场和隐式溶剂法的比较研究

静电极化在确定有机固体中载流子的能级方面起着重要作用，这受AMOEBA可极化力场中的原子极化率控制。基于QTAIM的分子极化率空间划分用于均匀地参数化π共轭有机小分子的状态特异性原子极化率（SSAP），以避免拟合某些人工训练集的分子极化率。在此，SSAP用于显式外推静电极化能量（E ^pol）9种π共轭有机晶体的载流子，其中包括6种p型转移材料，低聚并烯和TIPS取代的低聚并烯，以及3种n型转移材料，F取代的低聚并烯和TCNQ。我们的研究结果表明，该空穴载流子（的静电极化能量ë ₊ ^POL）是比所述电子载流子（小ë _- ^POL）对于p型分子，而Ë ₊ ^POL比较大ë _- ^POL为n型的分子。基于SSAP的E ^pol随着共轭长度的增加，低聚苯乙炔的值表现出几乎不变的特征，这与隐式可极化连续体模型（PCM）结果相似，而从默认原子极化率获得的E ^pol表现出明显的下降。隐式PCM可以正确捕获本体系统中大部分离子的静电极化，尽管它稍微低估了低并苯晶体中空穴和电子载流子之间的静电极化的间隙。我们的结果表明，这种统一的参数化SSAP提供了一种可靠且便宜的工具来估算冷凝相有机固体中载流子的能级。