Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge, United Kingdom.
J Phys Chem A. 2011 Nov 24;115(46):13684-93. doi: 10.1021/jp208088s. Epub 2011 Oct 21.
In this work we assess a recently published anisotropic potential for polycyclic aromatic hydrocarbon (PAH) molecules (J. Chem. Theory Comput. 2010, 6, 683-695). Comparison to recent high-level symmetry-adapted perturbation theory based on density functional theory (SAPT(DFT)) results for coronene (C(24)H(12)) demonstrate the transferability of the potential while highlighting some limitations with simple point charge descriptions of the electrostatic interaction. The potential is also shown to reproduce second virial coefficients of benzene (C(6)H(6)) with high accuracy, and this is enhanced by using a distributed multipole model for the electrostatic interaction. The graphene dimer interaction energy and the exfoliation energy of graphite have been estimated by extrapolation of PAH interaction energies. The contribution of nonlocal fluctuations in the π electron density in graphite have also been estimated which increases the exfoliation energy by 3.0 meV atom(-1) to 47.6 meV atom(-1), which compares well to recent theoretical and experimental results.
在这项工作中，我们评估了最近发表的一种用于多环芳烃 (PAH) 分子的各向异性势能（J. Chem. Theory Comput. 2010, 6, 683-695）。与最近基于密度泛函理论的基于对称性自适应微扰理论 (SAPT(DFT)) 的 coronene (C(24)H(12)) 的结果进行比较，证明了该势能的可转移性，同时突出了简单点电荷描述静电相互作用的一些局限性。该势能还能够非常准确地再现苯 (C(6)H(6)) 的第二维里系数，通过使用静电相互作用的分布式多极模型可以进一步增强这种准确性。通过 PAH 相互作用能的外推，估算了石墨烯二聚体相互作用能和石墨的剥离能。还估计了石墨中π 电子密度的非局域涨落的贡献，这将剥离能增加到 47.6 meV 原子(-1)，与最近的理论和实验结果相当。
