Alt Title

Thermochemistry and reaction dynamics of dinitrosoamide and hypohalous anions

Publication Date

2000

Document Type

Dissertation/Thesis

Degree Name

M.S. (Master of Science)

Department

Department of Chemistry and Biochemistry

LCSH

Mass spectrometry||Afterglow (Physics)||Thermochemistry||Anions

Abstract

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.

Comments

Includes bibliographical references (pages [87]-90)

Extent

viii, 90 pages

Language

eng

Publisher

Northern Illinois University

Rights Statement

In Copyright

Rights Statement 2

NIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors.

Media Type

Text

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