Ma. Vincent et al., The potential energy surfaces of N2O2 species: implications for selective catalytic reduction, PCCP PHYS C, 2(4), 2000, pp. 707-714
Stationary structures, both minima and transition states, on the potential
energy surface of N2O2 have been determined using large basis sets and high
levels of theory. Minima have been found at the ab initio [BD(T)] and dens
ity functional theory (B3LYP) levels, and transition structures have been l
ocated at the latter level. These calculations have allowed reaction pathwa
ys to the formation of O-2 and N-2 to be explored. A likely initial interme
diate is a non-cyclic covalently bound dimer with a barrier to formation su
fficiently low to suggest that it might be a candidate for a catalytic mech
anism. Subsequent steps towards N-2 and O-2 involve larger barriers, so tha
t substantial catalytic activation would be required for them to be involve
d in a facile reaction mechanism.