The three-body dissociation dynamics of Cl2O at 248 and 193 nm

The photodissociation of Cl2O has been studied at 248 and 193 nm using photofragment translational spectroscopy (PTS) experiments with tunable VUV photoionization detection. The sole products observed were Cl, 0 and ClO fragments. Based on the derived translational energy distributions for the ClO and Cl photofragments we conclude that at 248 nm 15% Of Cl2O excitation results in three-body dissociation. At 193 run no Cl-2 fragments are observed and we conclude that the oxygen atoms arise solely from three-body dissociation. Dissociation geometries derived from forward convolution fitting suggest two qualitatively distinct three-body dissociation pathways: asymmetric concerted dissociation and symmetric concerted dissociation in agreement with recent theoretical predictions. (C) 2009 Elsevier B.V. All rights reserved.