Structure of [18]Annulene Revisited: Challenges for Computing Benzenoid Systems

Le résumé fourni par la source

High Resolution Image Download MS PowerPoint Slide For cyclic conjugated structures, erratic computational results have been obtained with Hartree–Fock (HF) molecular orbital (MO) methods as well as density functional theory (DFT) with large HF-exchange contributions. In this work, the reasons for this unreliability are explored. Extensive computations on [18]annulene and related compounds highlight the pitfalls to be avoided and the due diligence required for such computational investigations. In particular, a careful examination of the MO singlet-stability eigenvalues is recommended. The appearance of negative eigenvalues is not (necessarily) problematic, but near-zero (positive or negative) eigenvalues can lead to dramatic errors in vibrational frequencies and related properties. DFT approaches with a lower HF admixture generally appear more robust in this regard for the description of benzenoid structures, although they may exaggerate the tendency toward planarity and C–C bond-equalization. For the iconic [18]annulene, the results support a nonplanar equilibrium structure. The density-fitted frozen natural orbital coupled-cluster singles and doubles with perturbative triples [DF-FNO CCSD(T)] method of electron correlation with an aug-pVQZ/aug-pVTZ basis set places the C 2 global minimum 1.1 kcal mol –1 below the D 6 h stationary point.

Ce résumé expose les affirmations des auteurs. BNTIC ne l’interprète pas comme une validation indépendante des résultats.