Observation of highly energetic collisions in classical trajectory studies of collisional energy transfer

The importance of collisions transferring large amounts of vibrational energy to and from highly vibrationally excited molecules is studied. In single collisions of hot CS₂ with different collision partners (CO, Ar, HCl, CH₄) up to 40 kcal/mol can be transferred. The relative importance of such "supercollisions" is small, but they can be observed in several phenomena. We show that the largest energy transfer does not correlate directly with either the initial CS₂ energy for low-order moments of the vibrational energy transfer distribution.