O(1D) + N2O Reaction: NO Vibrational and Rotational Distributions

Abstract

The O((1)D) + N(2)O → 2NO(X (2)Π) reaction has been studied in a molecular beam experiment in which O(3) and N(2)O were coexpanded. The precursor O((1)D) was prepared by O(3) photodissociation at 266 nm, and the NO(X (2)Π) molecules born from the reaction as the O((1)D) recoiled out of the beam were detected by 1+1 REMPI over the 220-246 nm probe laser wavelength range. The resulting spectrum was simulated to extract rotational and vibrational distributions of the NO(X (2)Π) molecules. The product rotational distribution is found to be characterized by a constant rotational temperature of ≈4500 K for all observed bands, v = 0-9. An inverted vibrational distribution is observed. A consistent explanation of this and previous experimental results is possible if there are two channels for the reaction, one producing a nearly statistical vibrational distribution for low O((1)D)-N(2)O relative velocity collisions and a second producing the inverted distribution observed here for high relative velocity collisions. The former might correspond to an insertion/complex-formation reaction, while the latter might correspond to a stripping reaction. Velocity relaxation of the O((1)D) is argued to compete strongly with reaction in most bulb studies, so that these studies see predominantly the nearly statistical distribution. In contrast, the beam experiments do not detect the part of the vibrational distribution produced in low relative velocity reactions because the O((1)D) is not relaxed from its initial velocity before it either reacts or leaves the beam.