Use of the CNDO Method in Spectroscopy. III. Monosubstituted Benzenes and Pyridines

Abstract

The modified CNDO method previously reported has been applied to the calculation of a series of monosubstituted benzenes and pyridines, namely, aniline, anilinium ion, benzonitrile, nitrosobenzene, phenol, phenoxide ion, toluene, pyridinium ion, pyridine-N-oxide, 1-hydroxy-pyridinium ion, the aminopyridines, and the cyanopyridines. The calculated values of the transition energies and corresponding oscillator strengths are in good agreement with available experimental data on the electronic spectra of these compounds. An analysis of the lower-energy excited states by means of the calculated results suggests that there is an astonishingly small amount of charge-transfer character associated with the observed ultraviolet bands. The calculations indicate that the changes in charge densities in going from the ground state to the lowest energy π → π* excited state can be related to the Hammett σ's for the substituents.