RECOMBINATION REACTIONS OF ATOMIC CHLORINE IN INERT-GASES - A VIBRATIONALLY RESOLVED TRANSIENT KINETICS STUDY AT PRESSURES BELOW 1ATM

The chlorine atom recombination reactions in the buffer gases of chlor ine, argon, nitrogen, and carbon dioxide below 1 atm pressure were stu died by the laser photolysis/chemiluminescence detection technique. Th e vibrationally resolved transient chemiluminescence spectra were reco rded. A reaction mechanism which included recombinations, electronic q uenching, and vibrational energy relaxation processes of both the A an d B excited states of the chlorine molecules was proposed to account f or the present experimental observations and also the related experime ntal results reported in the literature. Under the approximation of th e exponential energy-gap rate laws for the rate constants of the inter -and intraelectronic vibrational energy relaxations as proposed in the literature, either the rate constants of electronic quenching, vibrat ional relaxation within the same electronic states, and interelectroni c vibrational energy transfer between the A and B states of the chlori ne molecules by the buffer gases were determined or their upperbound v alues were estimated. The long-time steady state behavior of the mecha nism was also analyzed analytically and numerically.