THEORETICAL MECHANISTIC STUDY ON THE RADICAL-NEUTRAL REACTION OF CH(X²Π) WITH CH²CO

Abstract

A theoretical survey on the potential energy surface for the CH (X2Π) + CH2CO reaction has been carried out. The geometries and energies of all stationary points involved in the reaction are calculated at the UB3LYP/6-311+G(d, p) level. And the more accurate energy information is provided by single point calculations at the UCCSD(T)/6-311++G(2d, 2p) level. Relationships of the reactants, transition states, intermediates, and products are confirmed by the intrinsic reaction coordinate (IRC) calculations. Our calculations demonstrate that this reaction is most likely initiated by carbon-to-olefinic carbon attack manners. The results suggest that P1 (C2H3 + CO) is the most important product through two competitive channels R → IM1 → TS1/P1 → P1 (C2H3 + CO) and R → IM1 → TS1/6 → IM6 → TS6/P1 → P1 (C2H3 + CO) . This study presents highlights of the mechanism of the title reaction, which is in good agreement with experimental results.

Mechanism and Rate Constants of the CH3+ CH2CO Reaction: A Theoretical Study

“…These hydrocarbons are easily detected by gas analysis, whereas methylidyne CH, triplet 3 CH 2 , and singlet 1 CH 2 can be detected using laser‐induced fluorescence; hence their rate constants with ketene were measured experimentally in , and , respectively. Theoretically, these reactions with CH and CH 2 were addressed in and , respectively. Rate constants of the ketene reactions with other radicals in the current kinetic models were either approximated or derived from experiments a few decades ago and were not reevaluated more recently by advanced up‐to‐date theoretical methods.…”

Mechanism and rate constants of the CH2 + CH2CO reactions in triplet and singlet states: A theoretical study

“…A considerable amount of works, both theoretical and experimental, has been devoted to this issue. In particular, the reaction of ketene with a hydrogen atom has been studied most extensively and the attention of researchers has been also paid to the reactions with oxygen atom and various radicals and molecules, such as methyl, methylidyne, methylene (both in triplet and singlet states), CN radical, ozone, and hydroxyl radical OH . However, most of these papers were published long ago and the results were obtained based on the capabilities of the experimental and theoretical techniques available at that time.…”