Nonstatistical dynamics in deep potential wells: a quasiclassical trajectory study of methyl loss from the acetone radical cation.
The loss of methyl radical from the acetone radical cation, following its formation from the enol isomer, has been found to be nonergodic. The origins of this behavior are probed computationally by a quasiclassical trajectory simulation on an AM1-SRP potential energy surface. Experimental reaction outcomes are qualitatively reproduced, and evidence is presented that coherent excitation of the CCO angle bending during isomerization is a significant factor in the nonstatistical behavior.
Department of Chemistry, Baker Laboratory, Cornell University, Ithaca, New York 14853-1401, USA.
Jeremiah A
JA
Nummela
Barry K
BK
Carpenter