Competition between two- and three-body decay of Cl2O

The photodissociation dynamics of Cl2O at 235nm and 207nm are investigated. The chlorine atoms generated via dissociation into the radical and three-b ody decay channel are detected state specifically in a (2+1)-REMPI process. At 235nm the Cl2O molecule was excited to the 1(2)B(1) state and the decay is dominated by the radical dissociation Cl2O+h nu --> ClO+Cl. At 207nm an excitation into the 2(1)A(1) state takes place, which dissociates predomin antly into the three-body channel Cl2O+h nu --> 2Cl+O. The three-body decay is characterized based on the fragment kinetic energy distributions at 235 nm and 207nm. The shape of the energy distributions points to an asynchrono us concerted decay mechanism. (C) 2001 Elsevier Science Ltd. All rights res erved.