A generally accepted principle of chemical kinetics is that a reaction will be very slow at low temperatures if there is an activation barrier on the potential energy surface to form products. However, this Account shows that the reverse is true for gas-phase hydrogen abstraction reactions of the hydroxyl radical, OH, with organic molecules with which it can form a weakly bound (5–30 kJ mol⁻¹) hydrogen-bonded complex. For hydrogen atom abstraction reactions of OH with volatile organic compounds (VOCs) containing alcohol, ether, carbonyl, and ester functional groups, the reaction accelerates rapidly at very low temperatures, with rate coefficients, k, that can be up to a 1000 times faster than those at room temperature, despite the barrier to products. The OH radical is a crucial intermediate in Earth’s atmosphere, combustion processes, and the chemistry of the interstellar medium, where temperatures can reach as low as 10 K, so this behavior has very important implications for gas-phase chemistry in space. The key point is that at low temperatures the lifetime of the OH–VOC complex against re-dissociation back to reactants becomes much longer, and hence the probability of quantum mechanical tunneling under the reaction barrier to form products becomes much higher.
These observations were made possible by using Laval nozzles to generate uniform supersonic flows at extremely low temperatures so that condensation of the reagents at reactor walls is avoided. In this Account, the use of laser flash-photolysis combined with laser-induced fluorescence spectroscopy within Laval flows is described to study the unusual kinetics of this type of reaction at temperatures down to 21 K and demonstrate the rapid upturn in the rate coefficient. For the reaction of OH with CH₃OH, further evidence for the precomplex and tunneling mechanism comes from observation of the CH₃O reaction product at very low temperatures, despite it being formed over the higher barrier to reaction. The experimental observations are supported by theoretical calculations using the MESMER master equation package to calculate k(T) and product yields as a function of temperature and which make use of potential energy surfaces determined using ab initio methods. The CH₃O product is formed over a narrower barrier with a larger imaginary frequency and is calculated to be the sole product at very low temperatures. The kinetics of the OH reaction with CH₃OH were measured to be independent of pressure, consistent with a tunneling mechanism rather than any collisional stabilization of the prereactive complex. In this Account, we collate available kinetic data and show that this newly discovered mechanism for H atom transfer reactions appears to be generally applicable for reactions of OH with organic molecules containing oxygenated functional groups, which have been observed in space by radio-astronomy. Rather than being ignored for a range of interstellar environments, these OH reactions are now being included in chemical networks in space and have been shown to significantly influence the abundance of OH, the organic molecules themselves, and reaction products and provide novel routes to forming even more complex functional groups, for example, precursors to prebiotic molecules.
CORE (COnnecting REpositories)
CORE (COnnecting REpositories)