Mechanisms of the reaction of positive atomic oxygen ions with nitrogen
Journal Article
·
· J. Am. Chem. Soc.; (United States)
Mechanisms have been established for the state-to-state reaction O/sup +/(/sup 4/S/sub u/) + N/sub 2/(chi/sup 1/..sigma../sub g//sup +/) ..-->.. N(/sup 4/S/sub u/) + NO/sup +/(chi/sup 1/..sigma../sup +/) + 1.1 eV in terms of potential energy hypersurface characteristics for the relevant N/sub 2/O/sup +/ electronic states. The surface characteristics are established from ab initio excitation energy calculations at 180/sup 0/ and 130/sup 0/ along with limited scans of the 1/sup 4/A'', potential energy hypersurface. From these results and orbital considerations, adiabatic correlation diagrams are drawn, with emphasis on the quartet states, for C/sub infinity upsilon/ and C/sub s/ symmetry. The main mechanism is then shown to be adiabatic reaction governed by the potential energy hypersurface of the N/sub 2/O/sup +/ 1/sup 4/A'' state. The energy barrier and the extended value of R*/sub NN/ relative to the outer anharmonic turning point for N/sub 2/(upsilon), upsilon = 0 or upsilon = 1, 1.15, or 1.18 A, require that reaction on the 1/sup 4/A'' hypersurface exhibit ''threshold'' behavior for either translational or vibrational excitation of the reagents. It is also established that the N/sub 2/O/sup +/ quartet states above 1/sup 4/A'' play a net negative role--collisions reaching them tend to yield products other than N(/sup 4/S/sub u/) + NO/sup +/(chi/sup 1/..sigma../sup +/). A low-energy multistate mechanism is also shown to be possible for this state-to-state reaction. The 1/sup 4/A''(N/sub 2/--O)/sup +/ polarization state is shown to have an equilibrium geometry (R/sub NN//sup e/, R/sub NO//sup e/, A/sub NNO//sup e/) = (1.10 +- 0.01 A, 2.35 +- 0.10 A, 180/sup 0/) with a binding energy D/sup 0/(N/sub 2/--O/sup +/) = 0.48 +- 0.1 eV and k(N/sub 2/--O/sup +/) = 0.33 +- 0.05 mdyn/A.
- Research Organization:
- Argonne National Lab., IL
- OSTI ID:
- 5153395
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 100:4; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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