Photoelectron Spectra and Sum Rule Consideration. Higher Alkyl Amines and Alcohols

Photoelectron spectra of higher alkyl amines and alcohols (Me, Et, n- and i-Pr, and n-Bu) have been measured with the 584 A line of helium. Seven photoelectron bands corresponding to p-type MO’s were identified for ethylamine and ethanol. Nine bands were observed for n- and i-propylamine and n- and i-propanol, and eleven for n-butylamine and n-butanol, in addition to the first C2s bands appearing at about 19 eV. The sum rule previously proposed by Kimura et al. has further been applied to the compounds studied here. Total sums of vertical ionization energies in the region below 18 eV have been found to be well reproduced by the sums of appropriate energies estimated for the p-type localized MO’s, using Koopmans’ theorem. Information on orbital character has also been obtained from the sum rule in each symmetry species.