Methyl Loss from Acetone Radical Cation

1 Methyl Loss from Acetone Radical Cation The loss of a methyl 

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Trajectories initiated from the vicinity of acetone radical cation showed essentially equal loss of either methyl (branching ratio 1.01 0.01). In contrast, the branching ratio observed for methyl loss in trajectories originating the TS was 1.13 0.01, which is in qualitative agreement with the experimental values of 1-1,4.24 When the trajectories were divided into time courses, with a resolution of 5fs, a unique phenomenon appeared that the newly created methyl dissociated predominantly at very short reaction time intervals. It was found that the trajectories that would lose the newly formed methyl at very short times never entered the PES minimum of the acetone radical cation. The shortest duration trajectories simply took the exit without ever attaining the equilibrium geometry of the radical cation. 

Nummela, J. A. Carpenter, B. K. Nonstatistical dynamics in deep potential wells A quasiclassical trajectory study of methyl loss from the acetone radical cation, J. Am. Chem. Soc. 2002,124, 8512-8513. 

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