Electronic spectroscopy of propadiene (allene) by electron impact

Abstract

The electron impact excitation of propadiene (allene) has been studied experimentally at impact energies of 20, 40, and 60 eV and scattering angles from 6° to 80°. Two transitions with maxima at 4.28 and 4.89 eV are identified as singlet → triplet excitations. The magnitude of the splitting between these transitions is a measure of the interaction between the two perpendicular π molecular orbitals. The significance of these triplet excited states in the interpretation of previous electronic energy transfer experiments and sensitized photochemical studies is briefly discussed. Two very weak transitions are observed between 5.0 and 6.5 eV. The angular dependence of the corresponding cross sections indicates that these are spin‐allowed but symmetry‐forbidden transitions. A weak singlet → singlet transition is seen with a maximum at 6.74 eV. This feature has also been optically observed and attributed to an electric dipole‐allowed ? 1 A 1→1 1 E transition. This assignment is discussed in the light of the present results. The first strong transition, the ? 1 A 1→1 1 B 2 π→π* transition, appears with a maximum at 7.24 eV. Higher energy‐loss features between 7.95 and 10 eV probably involve excitations to Rydberg states. A previously unreported transition to a superexcited state is observed with a maximum at 11.25 eV.