Critical analysis of the local aromaticity concept in polyaromatic hydrocarbons.
A large number of local aromaticity indices for the benzenoid rings in polyaromatic hydrocarbons is computed. The results are interpreted, supporting Clar's hypothesis, and mutual correlations are investigated. It is shown that there are good correlations between all indices that strictly allow comparing benzenoid character. Poor correlations are found with NICS. A rationale is offered, yielding the conclusion that NICS and ring current maps follow a fundamentally different path to local aromaticity. In this sense the lack of correlation is not due to a real multidimensional character of aromaticity but rather to confusion and vagueness of the aromaticity concept.
Bultinck
Patrick
P
Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 (S3), B-9000 Gent, Belgium. Patrick.Bultinck@UGent.be