A comparative effect of ring annelation on cation-benzene and anion-benzene

DFT/B3LYP calculations were carried Out on several pi-complexes formed by cations and anions with annelated benzene, respectively. The binding energies obtained with standard method were corrected by basis set superposition error (BSSE) and zero-point energy (ZPE) during the geometry optimization for all complexes at the same levels of theory, respectively. Some different aspects of the pi-cation have been compared to those of pi-anion, involving in binding energy changes in effect of ring annelation, the aromaticity of the ring upon complexation, Mulliken and NBO charge-transfer. The effect of BSSE correction during the optimization is very important in some pi-anion complexes whether or not using diffuse functions in basis set. and results with at least one set of diffuse functions 6-31+G(d) basis set is a little better than results obtained by 6-31G(d, p) basis set for some pi-anion especially for F- complexes. (c) 2008 Elsevier B.V. All rights reserved.