HEI PHOTOELECTRON SPECTROSCOPIC (PES) STUDIES OF THE ELECTRONIC-STRUCTURE FOR ALKYL NITRITES CH3(CH2)(N)ONO (N=0, 1, 2, 3)

The HeI photoelectron spectra (PES) of alkyl nitrites CH3(CH2)(n)ONO, where n = 0, 1, 2, or 3, have been measured. Because of the high react ivities, the walls of the sample chamber and the ionization cell were coated with a dry graphite film and the inlet system was made of quart z. Ab initio calculations were performed at the 86 6-31G level. The d ecrease in the lowest-energy ionization potential and in the energy in terval between the two lowest-energy ionization potentials, which occu rs as n increases, can be considered as reflecting the large O-N-O cha racter of the two corresponding MOs, the HOMO and the SHOMO, and the e lectron-donating characteristics of the alkyl groups.