Potential energy surface single-product channels

The potential energy surface [47] for this reaction (Fig. 5) shows many potentially competitive pathways, labeled A-F, leading to the two most exothermic product channels. Many of these pathways can be isotopically separated by reaction of 02 with HCCO in normal abundance, as diagramed in Fig. 5. Zou and Osbom used time-resolved Fourier transform emission spectroscopy to detect the CO and CO2 products of this reaction [47]. Rotationally resolved infrared (IR) spectroscopy can easily identify all the possible isotopologs. For example. Fig. 6 shows a single... 

The study of multiple pathways leading to a single product channel provides a stringent test of our understanding of the potential energy surface and the calculations that use it to predict reaction outcomes. Although there are not many examples to date of pathway competitions, the increasing prominence of such systems, coupled with advances in experiment and theory that facilitate their study, promises a rich future in this normally hidden facet of reaction mechanisms. 

Combinations of wells and barriers may be used to model more complex potential-energy surfaces. In the examples we considered both reactivity and energy disposition were significantly affected by the position and nature of a single well or barrier. Further structure in the potential surface, such as placing steps in both reactant and product channels,... 

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