Thermochemistry and reaction dynamics of dinitrosoamide and hypohalous anions
M.S. (Master of Science)
Department of Chemistry and Biochemistry
Mass spectrometry||Afterglow (Physics)||Thermochemistry||Anions
N3O2' has been formed by the addition of 0.4 Torr N2O to a flowing afterglow apparatus. Energy-resolved collision-induced dissociation of this anion gives NO* as the dominant product. O' and N2O' are also observed, and there is indirect evidence for electron detachment. The N0"-N20 bond energy at 0 K is measured to be 0.76 ±0.10 eV. Ab initio calculations at the MP2/aug-cc-pVDZ level give a bond strength of 0.68 eV, in good agreement with the experimental results. The predominance of NO' over N20 ' is consistent with a metastable N20" anion. The results suggest that the photodissociation of N3O2' gives highly internally excited products. The hypohalous anions (XO', where X = F, Cl, Br, and I) have been formed in a flowing afterglow tandem mass spectrometer by energy-resolved collision of a halide ion beam with 0 2, N02, and N20 target gases. Several of these collisional reactions show large barriers to the formation of the XO' anion under these conditions. The barriers can be characterized by comparing the values obtained from these experiments with the well-known heats of formations for these systems.
Torchia, John William, "Flowing afterglow energy resolved mass spectrometry : the thermochemistry and reaction dynamics of dinitrosoamide and hypohalous anions" (2000). Graduate Research Theses & Dissertations. 3155.
viii, 90 pages
Northern Illinois University
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