Electronic spectroscopy of t r a n s-azomethane by electron impact

Abstract

The electron impact excitation of trans‐azomethane (i.e., trans‐dimethyl diazine CH₃–N–N–CH₃) has been studied by both trapped electron (TE) and differential electron scattering (DES) techniques. The nature of the excited state in each of several transitions has been identified by the energy and angular dependences of the excitation cross section. Two previously unreported singlet→triplet transitions are observed with maxima at 2.75 and 4.8₄ eV. Theoretical calculations on the parent compound, trans‐diimide (H–N=N–H), suggest that these are the ? ¹A_g→1 ³B_g (produced by excitation of an electron from an n₊ molecular orbital to a π* molecular orbital) and the ? ¹A_g→1 ³B_u (π→π*) transitions, respectively. The ? ¹A_g→1 ¹B_g (n₊→π*) transition is observed with a peak at 3.50 eV in the DES studies. A strong peak at 6.01 eV in the TE spectra appears as a weak shoulder in the DES studies and is interpreted as either a symmetry‐forbidden or Rydberg‐like singlet→singlet transition. Allowed singlet→singlet features overlap each other in the transition energy range from 6 to 10 eV. Peaks are seen in the DES spectra at 6.71, 7.8, and 9.5 eV and in the TE spectrum at 8.0 eV. Several significant differences between the TE and the DES spectra are analyzed on the basis of the different nature of the two experiments.