Understanding reactivity at very low temperatures: the reactions of oxygen atoms with alkenes.
A remarkable number of reactions between neutral free radicals and neutral molecules have been shown to remain rapid down to temperatures as low as 20 kelvin. The rate coefficients generally increase as the temperature is lowered. We examined the reasons for this temperature dependence through a combined experimental and theoretical study of the reactions of O(3P) atoms with a range of alkenes. The factors that control the rate coefficients were shown to be rather subtle, but excellent agreement was obtained between the experimental results and microcanonical transition state theory calculations based on ab initio representations of the potential energy surfaces describing the interaction between the reactants.
Sabbah
Hassan
H
Institut de Physique de Rennes, Laboratoire PALMS, UMR 6627 du CNRS-Université de Rennes 1, Equipe Astrochimie Expérimentale, Bat. 11c, Campus de Beaulieu, 35042 Rennes Cedex, France.
Biennier
Ludovic
L
Sims
Ian R
IR
Georgievskii
Yuri
Y
Klippenstein
Stephen J
SJ
Smith
Ian W M
IW