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Effects of an electric field on interaction of aromatic systems

The effect of uniform external electric field on the interactions between small aromatic compounds and an argon atom is investigated using post‐HF (MP2, SCS‐MP2, and CCSD(T)) and density functional (PBE0‐D3, PBE0‐TS, and vdW‐DF2) methods. The electric field effect is quantified by the difference of interaction energy calculated in the presence and absence of the electric field. All the post‐HF methods describe electric field effects accurately although the interaction energy itself is overestimated by MP2. The electric field effect is explained by classical electrostatic models, where the permanent dipole moment from mutual polarization mainly determines its sign. The size of π‐conjugated system does not have significant effect on the electric field dependence. We found out that PBE0‐based methods give reasonable interaction energies and electric field response in every case, while vdW‐DF2 sometimes shows spurious artifact owing to its sensitivity toward the real space electron density. © 2015 Wiley Periodicals, Inc.