Inductive and mesomeric effects on the π orbitals of halobenzenes

Abstract

Ionization potentials for the π bands of a wide range of fluoro-, chloro-, and bromobenzenes have been measured by the technique of photoelectron spectroscopy. An empirical model incorporating inductive and mesomeric terms is discussed and its validity tested with the observed energies. Satisfactory agreement is obtained with dipole moment data. The theory accurately predicts ionization energies only for molecules having no ortho halogen atoms. Deviations from linearity are adequately explained in terms of an ortho effect which is proportional to the number of halogens situated in ortho positions. An analogous effect has previously been observed in the electronic spectra of substituted benzenes. Application of the model to 1a _2u band shifts in the fluorobenzenes leads to the conclusion that the energy of this band in benzene lies in the region of 11·5 eV.