Reaction of O(1D) with Nitrogen

Publisher Website
Google Scholar
Abstract
Dilute solutions of O3 in liquid N2 have been photolyzed at several wavelengths in the ultraviolet with light from a monochromator. Nitrous oxide is formed in low quantum yield by reaction of O(1D) with the N2 solvent. Addition of an inert diluent, argon, does not lower the quantum yield, showing that the reaction is not due to ``hot atoms'' and probably has zero activation energy. The effect of added O2 on the N2O quantum yield shows that O2 reacts with O(1D) 4.5 times faster than does N2. The wavelength dependence of the N2O quantum yield suggests that the O(1D) quantum yield in the primary step of O3 photolysis is constant below about 3000 Å, but has a lower and apparently decreasing value above 3000 Å. In addition, exchange experiments with O236 show that the O(1D) yield is approximately unity at 3000 Å. The principal reaction of O(1D) with N2 is O(1D)+N2+M→N2+O(3P)+ M, and not O(1D)+N2+M→N2O+M. The low efficiency of N2O formation is due to a feature of the N2O potential energy surfaces which allows decomposition of the excited association complex to N2+O(3P), in the course of stepwise vibrational deactivation.

This publication has 8 references indexed in Scilit: