Vinoxy radical results

Indeed, by using soft El ionization, we have been able to unambiguously detect products from all five reaction pathways (2a)-(2e), determine their branching ratio and characterize their dynamics.34 Here we discuss some of the results that we have obtained on this reaction, which well exemplify the power of soft El ionization. First of all, from measurements of the El efficiency curves at various to/e ratios (15, 42, and 43), we have found that the parent ion at m/e = 43 (CH2CHO+, corresponding to one of the main reaction channels, the vinoxy radical,) is not stable, so measurements of angular and TOF distributions were carried out at m/e = 42. Incidentally, from the El ionization efficiency curve at m/e = 42 we have obtained some direct information on the IE of the vinoxy radical, for which no such information was available till now. The IE should be <11 eV. 

The nitroso-adduct ON-CH2CHO is formed by the attack of nitric oxide on the alkyl carbon atom of the radical. Addition of NO to the oxygen of the vinoxy radical CH2=CHO leads to the formation of CH2=CHONO. Results of ab initio calculations by Delbos et a/.182 show the occurrence of structural isomers of ON-CH2CHO and CH2=CHONO. Three structural stereoisomers of ON-CH2CHO have been found to correspond to the different orientations of the N-... 

This optimization was performed at the B3LYP/6-311G(d,p) level and the PES are illustrated in Figure 6.2. The resulting energies for the vinylperoxy radical (CH2=CHOO ) reaction to vinoxy + oxygen atom (CH2=CHO + O) are very close to those reported by Mebel et al. 

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