title: Quantitative Assessment of Aromaticity and Antiaromaticity Utilizing Vibrational Spectroscopy.
abstract: Vibrational frequencies can be measured and calculated with high precision. Therefore, they are excellent tools for analyzing the electronic structure of a molecule. In this connection, the properties of the local vibrational modes of a molecule are best suited. A new procedure is described, which utilizes local CC stretching force constants to derive an aromaticity index (AI) that quantitatively determines the degree of π-delocalization in a cyclic conjugated system. Using Kekulé benzene as a suitable reference, the AIs of 30 mono- and polycyclic conjugated hydrocarbons are calculated. The AI turns out to describe π-delocalization in a balanced way by correctly describing local aromatic units, peripheral, and all-bond delocalization. When comparing the AI with the harmonic oscillator model of AI, the latter is found to exaggerate the antiaromaticity of true and potential 4n π-systems or to wrongly describe local aromaticity. This is a result of a failure of the Badger relationship (the shorter bond is always the stronger bond), which is only a rule and therefore cannot be expected to lead to an accurate description of the bond strength via the bond length. The AI confirms Clar's rule of disjoint benzene units in many cases, but corrects it in those cases where peripheral π-delocalization leads to higher stability. [5]-, [6]-, [7]-Circulene and Kekulene are found to be aromatic systems with varying degree of delocalization. Properties of the local vibrational modes provide an accurate description of π-delocalization and an accurate AI.
authors.affiliation: Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University , 3215 Daniel Ave., Dallas, Texas 75275-0314, United States.
authors.forename: Dani
authors.initials: D
authors.lastname: Setiawan
authors.affiliation: Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University , 3215 Daniel Ave., Dallas, Texas 75275-0314, United States.
authors.forename: Elfi
authors.initials: E
authors.lastname: Kraka
authors.affiliation: Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University , 3215 Daniel Ave., Dallas, Texas 75275-0314, United States.
authors.forename: Dieter
authors.initials: D
authors.lastname: Cremer