Photodissociation of dicarbon: How nature breaks an unusual multiple bond

Abstract

The dicarbon molecule (C2) is found in flames, comets, stars, and the diffuse interstellar medium. In comets, it is responsible for the green color of the coma, but it is not found in the tail. It has long been held to photodissociate in sunlight with a lifetime precluding observation in the tail, but the mechanism was not known. Here we directly observe photodissociation of C2. From the speed of the recoiling carbon atoms, a bond dissociation energy of 602.804(29) kJ·mol−1 is determined, with an uncertainty comparable to its more experimentally accessible N2 and O2 counterparts. The value is within 0.03 kJ·mol−1 of high-level quantum theory. This work shows that, to break the quadruple bond of C2 using sunlight, the molecule must absorb two photons and undergo two “forbidden” transitions.