Er. Lovejoy et Cb. Moore, STRUCTURES IN THE ENERGY-DEPENDENCE OF THE RATE-CONSTANT FOR KETENE ISOMERIZATION, The Journal of chemical physics, 98(10), 1993, pp. 7846-7854
The isomerization of highly vibrationally excited and rotationally col
d ketene has been investigated by monitoring the (CO)-C-12 and (CO)-C-
13 dissociation products following laser excitation of jet-cooled (CH2
)-C-12 (CO)-13, (CH2)-C-13 (CO)-C-12, and (CD2)-C-12 (CO)-C-13. The ra
te constants for the reactions (CH2)-C-12 (CO)-C-13 half arrow right o
ver half arrow left (CH2)-C-13 (CO)-C-12 and (CD2)-C-12 half arrow rig
ht over half arrow left (CD2)-C-13 (CO)-C-12 are reported as a functio
n of energy with a resolution of 1 cm-1. The rate constants exhibit pr
onounced peaks as a function of energy near the reaction threshold. Th
is structure is attributed to quasistable motion along the reaction co
ordinate in the vicinity of the isomerization transition state.