物理化学学报2017，Vol.33Issue(4)：755-762,8.DOI:10.3866/PKU.WHXB201612292
卤素阴离子和取代苯间Anion-π作用强度的快速计算
A Scheme for Rapid Simulation of Anion-π Interactions Involving Halide Anions and Substituted Benzenes
摘要
Abstract
A scheme that explicitly contains electrostatic,polarization,and dispersion interactions to rapidly simulate anion-rr interactions is proposed and assessed by structural and energetic comparison with those produced via the complete basis set limit of the coupled-cluster singles and doubles plus perturbative triples [CCSD(T)/CBS] method for a set of X-…C6H6 nRn complexes where X-=F,Cl-,Br and R =CN,F.We use the chemical bonds C≡N,C-F,and C-H of the substituted benzenes as bond dipoles.The electrostatic interactions are estimated by calculating the interactions between the charge of the anion and the bond dipole moments of the substituted benzene.The polarization interactions are described according to the variation of the magnitudes of the bond dipole moments with the local environment.The parameters needed are produced by fitting the high-quality CCSD(T)/CBS potential energy curves.Calculation results show that our scheme produces equilibrium intermolecular distances with a root-mean-square deviation of 0.004 nm and interaction energies with a root-mean-square deviation of 2.81 kJ· mol-1 compared with the CCSD(T)/CBS results.The calculation results also show that our scheme reproduces the CCSD(T)/CBS potential energy curves well.These comparisons indicate the scheme proposed here is accurate and efficient,suggesting it may be a helpful tool to design and simulate relevant molecular materials.关键词
Anion-π作用/静电作用/极化作用/键偶极/相互作用能Key words
Anion-π interaction/Electrostatic interaction/Polarization/Bond dipole moment/Interaction energy分类
化学化工引用本文复制引用
王晓雯,李蕾,王长生..卤素阴离子和取代苯间Anion-π作用强度的快速计算[J].物理化学学报,2017,33(4):755-762,8.基金项目
The project was supported by the National Natural Science Foundation of China (21173109,21573098).国家自然科学基金(21173109,21573098)资助 （21173109,21573098）
