AM1 studies of photoelectron spectra

Abstract

Deep-lying π- and σ-orbitals of 10-alkylphenothiazines were studied by photoelectron spectroscopy and quantum-chemical AM1 calculations. It was demonstrated that in 10-ethylphenothiazine the lone electron pair of the S atom interacts with the π-system of the aromatic fragments. The π-MOs, whose energies are a function of the dihedral angle between the planes of the benzene rings of phenothiazines and are independent of the degree of pyramidality of the N atom, were found. The differences in the energy of these MOs were used for estimating equilibrium dihedral angles of tricyclic molecules in the gaseous phase. These values differ only slightly from those observed in the solid phase. The replacement of the hydrogen atom at position 10 by the methyl group leads to a decrease in the dihedral angle, leaving the orientation of the substituent unchanged. The orbital energies of phenothiazines, which were calculated by the AM1 method, adequately reflect the order of changes in the ionization potential. However, contributions of the two highest occupied π-MOs to the total charges on the N and S atoms are inconsistent with the experimental data.