Abstract

N2(A'Z2:), the lowest electronically excited state of NZ, has a long and distinguished history due to its role in nitrogen discharges and the nitrogen afterglow. Recently, the production of N,(A) via photolysis and chemiluminescent reactions has been newly explored, and new facets of its reactivity have been uncovered. Nz(A) is unusual, in that its deactivation probability in collision with small molecules spans many orders of magnitude, and is frequently strongly dependent on the vibrational content of NJA). This behavior and the observed product channels can be understood in terms of a simple model for the energy transfer process. Brief comparison with reactions of related species is made.

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The authors have investigated CO band emissions arising from the dissociative recombination of HCO(+) and HOC(+) ions with thermal electrons in a flowing afterglow plasma. The quantitative analysis of the band intensities showed that HCO(+) recombination forms the long-lived CO(a (3)Pi) state with a yield of 0.23+/-0.12, while HOC(+) recombination favors formation of CO(a' (3)Sigma(+)) and CO(d (3)Delta) with a combined yield of greater than 0.4. The observed vibrational distribution for the CO(a) state reproduces theoretical predictions quite well. The vibrational distributions for CO(a') and CO(d) are, in part, inverted, presumably as a consequence of a change in CO equilibrium bond length during recombination. The observations are compatible with current knowledge of the potential surfaces of states of HCO and HCO(+).