Mechanism of gas-phase decomposition of nitroethylene: A theoretical study

Calculations by the B3LYP density functional method with various basis sets and by the QCISD(T)/6-31G(d) ab initio method showed that the main pathway of monomolecular gas-phase decomposition of nitroethylene is that involving a cyclic intermediate, 4H-1,2-oxazete 2-oxide; the barrier of its formation (201.9, 203.9, and 216.5 kJ mol^–1, as estimated by various methods) reasonably agrees with the experimental value (191.9 kJ mol^–1). The barriers of alternative pathways of gas-phase decomposition of nitroethylene are considerably higher. The barriers of reactions involving radical cations are considerably lower than those of the similar reactions involving molecules. Among all the considered pathways of nitroethylene decomposition, bimolecular pathways are the most favorable energetically.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1327–1342.Original Russian Text Copyright © 2004 by Shamov, Nikolaeva, Khrapkovskii.This revised version was published online in April 2005 with a corrected cover date.