Temporary negative ions and electron affinities of benzene and N-heterocyclic molecules: pyridine, pyridazine, pyrimidine, pyrazine, and s-triazine

Abstract

Electron transmission spectroscopy is used to study shape resonances (temporary negative ions) in benzene and some isolectronic N−heterocyclic molecules (pyridine, diazines, and s−triazine), in the energy range 0−6 eV. The lowest shape resonance in each of these molecules exhibits vibrational structure which is interpreted in all cases as the totally symmetric C−C stretch mode. The ground vibrational level of this lowest shape resonance is accessible by electron impact only in benzene and pyridine. Thus, their electron affinities can be determined from the present experiment (−1.15 eV for C6D6 and −0.62 eV for C5H5N). Only excited vibrational levels are accessible in the diazines and s−triazine, indicating that the electron affinities for these molecules have positive values. For benzene, pyridine, and some other aromatic hydrocarbons, we compare the electron affinities established in the gas phase with the polarographic potentials established in the liquid phase and we find a linear relationship. Using this correlation in conjunction with the measured values of the polarographic potentials, we estimate the electron affinities for pyridazine (0.25 eV), pyrimidine (0 eV), pyrazine (0.40 eV) and s−triazine (0.45 eV).