Cooperative two-photon-induced chemical bond formation during a Kr+F2 collision to form KrF

The reactive Kr⁺F₂^? potential energy surface is probed by two-photon, laser-induced chemical bond formation during a Kr+F₂ collision. This is compared with the pulsed laser excitation (two-photon) of Kr(2p₉) followed by collision with F₂ leading to the formation of KrF(B, C). In addition to reporting the excitation spectrum for the two-phonon-induced collision process, these techniques were used to determine quenching rate constants of Kr₂F^*. Quenching by Xe gives XeF(B, C) with rate constant (1.5±0.2)×10^?10 cm³ s^?1; the quenching rate constant for F₂ is (1.5±0.2)×10^?10 cm³ s^?1, and the radiative lifetime of Kr₂F^* is 240±35 ns. The quenching rate constant for the coupled Kr(2p₈) and Kr(2p₉) levels by F₂ is (13±2)×10^?10 cm³ s^?1.