Condensed Aromatics. Part III. In-Plane Molecular Vibrations of Pyrene

Abstract

A new force field is developed for the in-plane vibrations of condensed aromatics using pyrene as a test molecule. Only five parameters are employed in this force field, which improves a four-parameter approximation previously investigated. Still the simple five-parameter approximation gives calculated vibrational frequencies in good agreement with those from the more elaborate Califano-Neto force field. In the course of the normal coordinate analysis the Hückel molecular orbitals have been deduced. The CC stretching parameters were modified by means of the calculated bond orders. A complete set of independent symmetry coordinates (both in-plane and out-of-plane) for the pyrene molecular model was developed. New experimental data from infrared and Raman spectra for pyrene are reported. Also the mean amplitudes of vibration are studied in detail. It is concluded that the simple five-parameter approximation gives reliable mean amplitudes, which undoubtedly are accurate enough for the interpretation of gas electron diffraction data. Finally the calculated frequencies and mean amplitudes of benzene are given. The mean amplitudes are again found to be very accurate in spite of some substantial inaccuracies in the frequencies. © 1979, Walter de Gruyter. All rights reserved.