15min:

ALEXEY L. KALEDIN, MICHAEL C. HEAVEN, KEIJI MOROKUMA, Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322; DANIEL M. NEUMARK, Department of Chemistry, University of California, Berkeley, CA 94720.

~An electron photodetachment spectrum of Cl₃^- is reported for 193 nm (6.42 eV) excitation. The spectrum was assigned using high-level ab initio calculations for the Cl₃ radical and the Cl₃^- anion. A broad band centered around 1.25 eV (electron kinetic energy) has been assigned to the Cl₃^-(X^{1 +}_g) Cl₃(X² _u) and Cl₃(1^{2 +}_g) transitions. Vertical photodetachment accesses the transition state region for the Cl exchange reaction: Cl + Cl₂ Cl₂ + Cl. A narrow doublet band at 0.55 eV is assigned to the Cl₃^-(X^{1 +}_g) Cl₃(1² _g) transition, split by spin-orbit interaction.