Dimethylamine Addition to Formaldehyde Catalyzed by a Single Water Molecule: A Facile Route for Atmospheric Carbinolamine Formation and Potential Promoter of Aerosol Growth.

We use ab initio calculations to investigate the energetics and kinetics associated with carbinolamine formation resulting from the addition of dimethylamine to formaldehyde catalyzed by a single water molecule. Further, we compare the energetics for this reaction with that for the analogous reactions involving methylamine and ammonia separately. We find that the reaction barrier for the addition of these nitrogen-containing molecules onto formaldehyde decreases along the series ammonia, methylamine, and dimethylamine.

Hydrolysis of ketene catalyzed by formic acid: modification of reaction mechanism, energetics, and kinetics with organic acid catalysis.

The hydrolysis of ketene (H2C═C═O) to form acetic acid involving two water molecules and also separately in the presence of one to two water molecules and formic acid (FA) was investigated. Our results show that, while the currently accepted indirect mechanism, involving addition of water across the carbonyl C═O bond of ketene to form an ene-diol followed by tautomerization of the ene-diol to form acetic acid, is the preferred pathway when water alone is present, with formic acid as catalyst, addition of water across the ketene C═C double bond to directly produce acetic acid becomes the kinetically favored pathway for temperatures below 400 K. We find not only that the overall barrier for ketene hydrolysis involving one water molecule and formic acid (H2C2O + H2O + FA) is significantly lower than that involving two water molecules (H2C2O + 2H2O) but also that FA is able to reduce the barrier height for the direct path, involving addition of water across the C═C double bond, so that it is essentially identical with (6.

UV photochemistry of peroxyformic acid (HC(O)OOH): an experimental and computational study investigating 355 nm photolysis.

The photochemistry of peroxyformic acid (PFA), a molecule of atmospheric interest exhibiting internal hydrogen bonding, is examined by exciting the molecule at 355 nm and detecting the nascent OH fragments using laser-induced fluorescence. The OH radicals are found to be formed in their ground electronic state with the vast majority of available energy appearing in fragment translation. The OH fragments are vibrationally cold (v" = 0) with only modest rotational excitation.