Transition state spectroscopy of the photoinduced Ca + CH(3)F reaction. 1. A cluster isolated chemical reaction study.

The "cluster isolated chemical reactions" technique is used to examine the dynamics of the photoinduced reaction producing electronically excited CaF when 1:1 Ca-CH(3)F complexes are deposited at the surface of large argon clusters. This technique ensures quantitatively that 1:1 complexes are actually at the origin of the observed signals. The reaction is monitored by observing the CaF chemiluminescence while scanning the photoexcitation laser. The resulting action spectrum contains information about the absorption bands of the complex, filtered by the dynamics of the reaction. The observations suggest a profound alteration of the calcium electronic structure and a control of the reaction by the CF stretch in CH(3)F.