Multiplex detection of collisional energy transfer using KCSFI

A new detection method for obtaining collisional transition probabilities P (E', E) of highly vibrationally excited molecules in the gas phase is presented. The technique employs energy-selective probing of the time-dependent vibrational population distribution by kinetically controlled selective fluorescence (KCSF). We present experimental results for a test system, the collisional deactivation of toluene by argon, where we use the well-known kinetically controlled selective ionization (KCSI) scheme as a reference for comparison. A newly designed setup is employed that allows simultaneous detection of fluorescence and ionization signals under identical experimental conditions ( kinetically controlled selective fluorescence and ionization = KCSFI). For the system toluene + argon it is demonstrated that KCSF and KCSI yield identical results. A rate-equation model is presented to understand common features and differences of both approaches. The fluorescence detection scheme shows promise for future investigations on collisional energy transfer. The experimental setup is simpler, because it requires no additional ionization wavelength. This will hopefully give access to the P ( E 0, E) of systems where, e. g., ionization schemes are difficult to implement due to short wavelengths required for the ionization step. A few examples will be outlined briefly.