Xu Tao, Wang Wenliang, Yin Shiwei, Wang Yun
Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an city, 710062, China.
Phys Chem Chem Phys. 2017 Jun 7;19(22):14453-14461. doi: 10.1039/c7cp01534h.
The solvated supermolecular approach, i.e., block-localized wave function coupled with polarizable continuum model (BLW/PCM), was proposed to calculate molecular ionization potential (IP), electron affinity (EA) in the solid phase, and related electronic polarization. Via the calculations of a solvated supermolecule (5M), including four closest molecules, BLW/PCM overcomes the limitation in the calculation for the monomer PCM, that is, nearly same electronic polarization for cation (P) and anion (P). The solvated supermolecular approach successfully described asymmetric behaviors of P and P for oligoacene crystals. In addition, we also compared two charge-localized methods, i.e., BLW and constrained density functional theory (CDFT), to calculate the molecular IP and EA in supermolecules with/without PCM. Our results demonstrate that both the BLW and CDFT correctly estimate the EA and IP values in the gas phase cluster, whereas CDFT/PCM fails to evaluate the P value of the bulk system.
提出了溶剂化超分子方法，即结合极化连续介质模型的块定域波函数（BLW/PCM），用于计算固相中的分子电离势（IP）、电子亲和势（EA）以及相关的电子极化。通过对包含四个最邻近分子的溶剂化超分子（5M）进行计算，BLW/PCM克服了单体PCM计算中的局限性，即阳离子（P）和阴离子（P）的电子极化几乎相同。溶剂化超分子方法成功地描述了并五苯晶体中P和P的不对称行为。此外，我们还比较了两种电荷定域方法，即BLW和约束密度泛函理论（CDFT），以计算有无PCM的超分子中的分子IP和EA。我们的结果表明，BLW和CDFT都能正确估计气相簇中的EA和IP值，而CDFT/PCM无法评估本体系统的P值。
