A Novel Mechanism for Nitric Oxide Production in Nitroalkyl Radicals that Circumvents Nitro-Nitrite Isomerization.
In this study, we present a novel mechanism for NO loss from nitroalkyl radicals that circumvents the traditional higher-energy nitro-nitrite isomerization. We characterize the intrinsic reaction coordinate at the B3LYP/6-311++g(3df,2p) level of theory and calculate the transition-state energies using the G4 composite method; the subsequent dynamics en route to the highly exothermic NO + acetone product channel proceeds through a three-membered ring intermediate. Crossed laser-molecular beam scattering experiments on the 2-nitro-2-propyl radical confirm the importance of this new mechanism in determining the product branching.
The James Franck Institute and Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Ryan S
RS
Booth
The James Franck Institute and Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Chow-Shing
CS
Lam
The James Franck Institute and Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Laurie J
LJ
Butler
B3LYP; isomerization; nitrite; nitro; nitroalkanes; radicals