Kinetics in Cold Laval Nozzle Expansions: From Atmospheric Chemistry to Oxidation of Biomolecules in the Gas Phase

Abstract

New developments and recent applications of pulsed and miniaturised Laval nozzle technology allowing many gas-phase molecular processes to be studied at very low temperatures are highlighted. In the present Minireview we focus on molecular energy transfer and reactions of molecular radicals (e.g. OH) with neutral molecules. We show that with the combination of pulsed laser photolysis and sensitive laser-induced fluorescence detection a large number of fast reactions of radicals with more or less complex neutral molecules can be measured in Laval nozzle expansions nowadays. It is also demonstrated that collisional energy transfer of neutral molecules can be measured via kinetically controlled selective fluorescence (KCSF) excitation down to 58 Kelvin. Finally, we show that even the primary steps in the oxidation of biomolecules or biomolecular building blocks initiated by OH radicals can be followed at low temperatures. The temperature dependence of the measured rate constants is the key for an understanding of the underlying molecular mechanisms and the Laval nozzle expansion provides a unique environment for these measurements. The experimental finding that many reactions between radicals and neutral species can be rapid at low temperatures are discussed in terms of pre-reactive complexes formed in the overall complex forming bimolecular reactions.