Ethylene Intersystem Crossing Caught in the Act by Photofragment Sulfur Atoms

Ethylene, C₂H₄, the simplest π-bonded molecule, is of enormous fundamental and commercial importance. Its lowest triplet state, in which the CH₂ moieties occupy perpendicular planes, is well known from theory, but there has been no definitive experimental observation of this species. Here, velocity map imaging of the sulfur atoms in ethylene sulfide (c-C₂H₄S) photodissociation at 217 nm is used to reveal the internal state distribution of co-product ethylene. While both S (¹D) and S (³P) translational energy distributions display three distinct regions that find their origins in singlet and triplet excited states of c-C₂H₄S, respectively, the S (³P) distribution is dominated by a fourth, low-recoil region. In this region, the distribution is fully isotropic at a recoil of 9 ± 1 kcal/mol, corresponding to the opening of the triplet ethylene channel. Multireference calculations suggest that this photodissociation pathway is mediated by a hot, transient biradical CH₂CH₂S that strongly favors CH₂-hindered rotations in the predissociated complex. This photochemical ring-opening mechanism is invoked to account for the vibrational features observed in this low-recoil region, which are attributed to triplet ethylene relaxing to the torsional saddle point on the ground-state singlet surface. This study thereby gives for the first time the experimental confirmation of an adiabatic singlet-triplet splitting of 66 ± 1 kcal/mol and a torsional barrier height of 64 ± 1 kcal/mol in ethylene.