A theoretical study on the mechanism of electronic to vibrational energy transfer in Hg(3P)+ CO collisions

Abstract

The mechanism of electronic‐to‐vibrational (E–V) energy transfer in Hg(³P) + CO collisions has been studied theoretically. The configuration interaction (CI) method was employed to calculate potential energy surfaces of the collision system. A simplified theoretical model, based on the reaction coordinate concept and the calculated potential energy characteristics, was used to discuss the mechanism of the singlet–triplet transition and the energy disposal in the collision. The results obtained were that: (a) the quenching process proceeds via a collision complex mechanism; and that (b) the triplet–singlet transition occurs near the collinear geometry. A model classical trajectory calculation gives a product CO vibrational distribution in good agreement with the experimental result.