堆积
范德瓦尔斯力
化学物理
均三甲苯
非共价相互作用
相互作用能
化学
二聚体
分子
分子物理学
计算化学
结晶学
苯
氢键
有机化学
作者
Montgomery Gray,John M. Herbert
标识
DOI:10.1021/acs.jpcc.2c08413
摘要
Parallel-displaced π-stacking in the benzene dimer and larger polycyclic aromatic hydrocarbons is driven by competition between dispersion and exchange-repulsion interactions. The present work examines whether the same is true in porous frameworks that exhibit stacking interactions, including the [18]annulene dimer, porphyrin dimer, and several models of the covalent organic framework known as COF-1. Interaction energies and their components are computed using extended symmetry-adapted perturbation theory along two-dimensional scans representing slip-stacking. As in the polycyclic aromatic hydrocarbons studied previously, we find that the van der Waals interaction potential (defined as the sum of dispersion and Pauli repulsion) drives the system into a slip-stacked geometry. Electrostatics is a relatively small component of the total interaction energy. In the case of COF-1, the van der Waals potential drives the conformational preference whether or not a solvent molecule intercalates into the framework, although the presence of the guest (mesitylene) molecule substantially limits the low-energy slip-stacking configurations that are available. Even when the COF-1 pore is empty, a modest lateral offset of ≲1.5 Å is preferred, which is small compared to the pore size.
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