Theoretical study of the reaction OH + acetone: a possible kinetic effect of the presence of water?

Single water-molecule catalysis in the glyoxal + OH reaction under tropospheric conditions: Fact or fiction? A quantum chemistry and pseudo-second order computational kinetic study

“…The apparent rate coefficient, taking into account the atmospheric water concentration (and therefore, the relative glyoxal-H 2 O complex concentration) is orders of magnitude smaller than the corresponding one in the gas phase. Actually, the importance of taking into account the concentration of the VOC-water complex was already mentioned by Canneaux et al [31]. in a theoretical study of the acetone + OH reaction, but it was ignored in several subsequent articles.…”

Odd‐hydrogen: An account on electronic structure, kinetics, and role of water in mediating reactions with atmospheric ozone. Just a catalyst or far beyond?

“…The findings (often conflicting) reported in the literature on the rate enhancement of radical reactions by a single or even a few water molecules must take into account the atmospheric abundance of the radical‐molecule complexes despite some catalytic role that is observed in the former. Indeed, studies have pointed out to the low tropospheric abundance of radical‐water complexes, thence suggesting that an atmospheric effect is unlikely .…”

“…The findings (often conflicting) reported in the literature on the rate enhancement of radical reactions by a single or even a few water molecules must take into account the atmospheric abundance of the radical‐molecule complexes despite some catalytic role that is observed in the former. Indeed, studies have pointed out to the low tropospheric abundance of radical‐water complexes, thence suggesting that an atmospheric effect is unlikely . This contrasts with documented important examples of single molecule catalysis such as the hydration of SO 3 , autocatalytic decomposition of sulfurous acid or carbonic acid and possibly with the HO 2 + O 3 reaction here highlighted .…”

“…Recent literature discusses the possibility that even a single water molecule may act as catalyst in gas‐phase by forming complexes with reactants, products or transition states with lowering of its energy . For example, studies have been reported on the catalytic activity by a single water molecule in OH reactions with methane, formic acid, acetaldehyde, propionaldehyde, H 2 O, methane sulfonic acid, glyoxal, acetone, the self‐reaction of HO 2, OH with HO 2, and HO 2 with O 3 . Of them, the water mediated acetaldehyde reaction with OH offers an interesting and controversial example.…”

Reactivity Trends in Radical-Molecule Tropospheric Reactions - A Quantum Chemistry and Computational Kinetics Approach

“…In fact, the kinetic effect of the presence of water had already been studied (Canneaux et al, 2004) in a theoretical study of the reaction of acetone with OH radicals in the presence of a single water molecule. Their conclusion was that the tropospheric concentration of OH-acetone-water complexes would be very small, but that they might still be detected experimentally.…”