Applications of H\"uckel-Su-Schrieer-Heeger method. I. Carbon-carbon bond lengths in polycyclic aromatic hydrocarbons

Abstract

The equilibrium carbon-carbon bond lengths in $\pi$-electron hydrocarbons are very sensitive to the electronic ground-state characteristic. In the recent two papers by Stolarczyk and Krygowski (to appear soon) a simple quantum approach, the Augmented H\"uckel Molecular Orbital (AugHMO) model, is proposed for the qualitative, as well as quantitative, study of this phenomenon. The simplest realization of the AugHMO model is the H\"uckel-Su-Schrieffer-Heeger (HSSH) method, in which the resonance integral $\beta$ of the HMO model is a linear function the bond length. In the present paper the HSSH method is applied in a study of carbon-carbon bond lengths in a set of 34 selected policyclic aromatic hydrocarbons (PAHs). This is exactly the set of molecules analyzed by Rieger and M\"ullen (\textit{J. Phys. Org. Chem.} \textbf{2010}, \textit{23}, 315) in the context of their electronic-excitation spectra. These PAHs have been obtained by chemical synthesis, but in most cases no diffraction data (by X-rays or neutrons) of sufficient quality is available to provide us with their geometry. On the other hand, these PAHs are rather big (up to 96 carbon atoms), and \textit{ab initio} methods of quantum chemistry are too expensive for reliable geometry optimization. That makes the HSSH method a very attractive alternative. Our HSSH calculations uncover a modular architecture of certain classes of PAHs. For the studied molecules (and their fragments -- modules) we calculate the values of the aromaticity index HOMA.