Acta Phys. -Chim. Sin. ›› 2017, Vol. 33 ›› Issue (4): 755-762.doi: 10.3866/PKU.WHXB201612292

• ARTICLE • Previous Articles     Next Articles

A Scheme for Rapid Simulation of Anion-π Interactions Involving Halide Anions and Substituted Benzenes

Xiao-Wen WANG,Lei LI,Chang-Sheng WANG*()   

  • Received:2016-11-02 Published:2017-03-23
  • Contact: Chang-Sheng WANG
  • Supported by:
    The project was supported by the National Natural Science Foundation of China(21173109);The project was supported by the National Natural Science Foundation of China(21573098)


A scheme that explicitly contains electrostatic, polarization, and dispersion interactions to rapidly simulate anion-π 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.

Key words: Anion-π interaction, Electrostatic interaction, Polarization, Bond dipole moment, Interaction energy