The Near-ultraviolet Absorption Spectrum of Diimide Vapor

Absorption spectra of N2H2 and N2D2 in the gas phase have been obtained in the region 3000–4300 Å, consisting of about 30 diffuse bands for each compound. Long progressions in the spectra are attributed to excitation of the H—N=N bending mode, v2′, in the upper state, with much shorter progressions arising from the N=N stretching mode, v3′; values of v2′ = 1215 and 910 cm−1 and v3′ = 1550 and 1440 cm−1 were estimated for N2H2 and N2D2 respectively.The spectra are attributed to the 1Bg ← 1Ag(π* ← n+) transition of trans diimide, probably made allowed by vibronic interaction. From Franck–Condon calculations the H—N=N angle in the upper state was estimated to be 132 ± 2°, an increase of 25° from the ground-state value; the increase in the N=N bond length was estimated to be about 0.05 Å.