Cl-3(-) electron photodetachment spectrum: measurement and assignment

An electron photodetachment spectrum of Cl-3(-) is reported for 193 nm (6.4 2 eV) excitation. The spectrum was assigned using high-level ab initio calc ulation for the Cl-3 radical and the Cl-3(-) ion. A broad band centered aro und 1.25 eV (electron kinetic energy) has been assigned to the Cl-3(-)(X (1 )Sigma(g)(+)) --> Cl-3(X (2)Pi(u)) and Cl3(1 (2)Sigma(g)(+)) transitions. V ertical photodetachment accesses the transition state region for the Cl exc hange reaction: Cl + Cl-2 --> Cl-2 + Cl. A narrow doubler hand at 0.55 eV i s assigned to the Cl-3(-)(X (1)Sigma(g)(+)) --> Cl3(1 (2)Pi(g)) transition, split by spin-orbit interaction. (C) 1999 Elsevier Science B.V. All rights reserved.