Quantum chemical investigation of reactions of atomic carbon with water and methanol

Dede, Yavuz
Reactions of singlet (1S and 1D) and triplet (3P) carbon atoms with water, and 1D and 3P carbon atoms with methanol were studied computationally. In the water and methanol systems, the carbon vapor containing a mixture of C(1S), C(1D), and C(3P) atoms, is predicted to react by primarily interacting with the oxygen, OH bond and CH bond of the substrate mainly with the 1D state. While C(1S) was proven to be unreactive C(3P) can hardly be supported to be reactive, and can safely be defined as unreactive. The major product, CO forms as a result of oxygen abstraction, which is observed as a fast, energetically quite favorable process. The scheme of this oxygen abstraction is promising to be applicable to substrates with the general formula R1-O-R2 i.e. water, alcohols, and ethers. OH insertion, both for water and methanol, yields trappable carbenes; the carbene being a key species on the distribution of the end products. Water matrix trapping the carbene opens the path to the formation of formaldehyde; and exhibits a prototype reaction for the formation of dialkoxymethanes. Gas phase product spectrum from the reactions are broader, due to the accessibility of the routes originating from the otherwise trapped intermediates; and the excess energy of the reactions being carried by them. In the condensed phase the very early and rapid reactions seem to have chance, the subsequent rearrangements are hard to occur. The conclusions thus far apply to the reactions in the gas phase as well as in condensed phases involving inert matrices; and the experimental isolation of the species is highly dependent on the ability of the medium to trap the intermediates via effective transfer of excess energy. Due to the large excess energies of intermediates involved, subsequent reactions are fast; of the order 1013 s-1 from kinetic rate calculations. In the absence of efficient transfer of non-fixed energies to the surrounding medium, all of the reaction paths will conclude with irreversible dissociation reactions. Plausible mechanisms for all the experimentally observed products are predicted. The results are in agreement with the available experimental data.
Citation Formats
Y. Dede, “Quantum chemical investigation of reactions of atomic carbon with water and methanol,” Ph.D. - Doctoral Program, Middle East Technical University, 2007.