Ion-molecule rate constants and branching ratios for the reaction of N(3) (+)+O(2) from 120 to 1400 K

• Published in: The Journal of chemical physics Vol. 121; no. 19; p. 9481
• Main Authors: Popovic, Svetozar, Midey, Anthony J, Williams, Skip, Fernandez, Abel I, Viggiano, A A, Zhang, Peng, Morokuma, K
• Format: Journal Article
• Language: English
• Published: United States 15.11.2004
• ISSN: 0021-9606
• DOI: 10.1063/1.1807376

The kinetics of the reaction of N(3) (+) with O(2) has been studied from 120 to 1400 K using both a selected ion flow tube and high-temperature flowing afterglow. The rate constant decreases from 120 K to approximately 1200 K and then increases slightly up to the maximum temperature studied, 1400 K. The rate constant compares well to most of the previous measurements in the overlapping temperature range. Comparing the results to drift tube data shows that there is not a large difference between increasing the translational energy available for reaction and increasing the internal energy of the reactants over much of the range, i.e., all types of energies drive the reactivity equally. The reaction produces both NO(+) and NO(2) (+), the latter of which is shown to be the higher energy NOO(+) linear isomer. The ratio of NOO(+) to NO(+) decreases from a value of over 2 at 120 K to less than 0.01 at 1400 K because of dissociation of NOO(+) at the higher temperatures. This ratio decreases exponentially with increasing temperature. High-level theoretical calculations have also been performed to compliment the data. Calculations using multi-reference configuration interaction theory at the MRCISD(Q)/cc-pVTZ level of theory show that singlet NOO(+) is linear and is 4.5 eV higher in energy than ONO(+). A barrier of 0.9 eV prevents dissociation into NO(+) and O((1)D); however, a crossing to a triplet surface connects to NO(+) and O((3)P) products. A singlet and a triplet potential energy surface leading to products have been determined using coupled cluster theory at the CCSD(T)/aug-cc-pVQZ level on structures optimized at the Becke3-Lee, Yang, and Parr (B3LYP)/aug-cc-pVTZ level of theory. The experimental results and reaction mechanism are evaluated using these surfaces.