Electron spin resonance and CNDO/2 study of the radicals produced during fast electron irradiation of substances containing nitrogen. Part 2.—Hydrazine

Abstract

The hydrazine cation and the hydrazyl radical have been observed during fast electron irradiation of liquid hydrazine adsorbed in a zeolite matrix.

The hydrazyl radical was identified and its structure investigated by comparing the results of e.s.r. measurements and CNDO/2 molecular orbital calculations. The radical can be described as having a trigonal nitrogen on one side and on the other a nitrogen with a geometry intermediate between trigonal and pyramidal. Restricted rotation about the N—N bond has been shown to be responsible for an alternating line width effect apparent in the e.s.r. spectrum.

The same considerations lead to the conclusion that the cation is probably planar at low temperatures but bent at high temperatures.