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J Chem Phys. 2008 Apr 14;128(14):144108. doi: 10.1063/1.2902974.

Intramolecular basis set superposition error effects on the planarity of benzene and other aromatic molecules: a solution to the problem.

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  • 1Institut de Química Computacional, Parc Científic i Tecnològic de la Universitat de Girona, Edifici Jaume Casademont, Pic de Peguera 15 la Creueta, 17003 Girona, Spain.


Recently, the surprising result that ab initio calculations on benzene and other planar arenes at correlated MP2, MP3, configuration interaction with singles and doubles (CISD), and coupled cluster with singles and doubles levels of theory using standard Pople's basis sets yield nonplanar minima has been reported. The planar optimized structures turn out to be transition states presenting one or more large imaginary frequencies, whereas single-determinant-based methods lead to the expected planar minima and no imaginary frequencies. It has been suggested that such anomalous behavior can be originated by two-electron basis set incompleteness error. In this work, we show that the reported pitfalls can be interpreted in terms of intramolecular basis set superposition error (BSSE) effects, mostly between the C-H moieties constituting the arenes. We have carried out counterpoise-corrected optimizations and frequency calculations at the Hartree-Fock, B3LYP, MP2, and CISD levels of theory with several basis sets for a number of arenes. In all cases, correcting for intramolecular BSSE fixes the anomalous behavior of the correlated methods, whereas no significant differences are observed in the single-determinant case. Consequently, all systems studied are planar at all levels of theory. The effect of different intramolecular fragment definitions and the particular case of charged species, namely, cyclopentadienyl and indenyl anions, respectively, are also discussed.

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