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Mass-Spectrometric Experiments together with Electronic Structure Calculations Support the Existence of the Elusive Ammonia Oxide Molecule and Its Radical Cation

  1. Mark Brönstrup,
  2. Detlef Schröder,
  3. Ilona Kretzschmar,
  4. Christoph A. Schalley,
  5. Helmut Schwarz

Article first published online: 7 DEC 1998

DOI: 10.1002/(SICI)1099-0682(199810)1998:10<1529::AID-EJIC1529>3.0.CO;2-Y

Issue

European Journal of Inorganic Chemistry

European Journal of Inorganic Chemistry

Volume 1998, Issue 10, pages 1529–1538, October 1998

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How to Cite

Brönstrup, M., Schröder, D., Kretzschmar, I., Schalley, C. A. and Schwarz, H. (1998), Mass-Spectrometric Experiments together with Electronic Structure Calculations Support the Existence of the Elusive Ammonia Oxide Molecule and Its Radical Cation. European Journal of Inorganic Chemistry, 1998: 1529–1538. doi: 10.1002/(SICI)1099-0682(199810)1998:10<1529::AID-EJIC1529>3.0.CO;2-Y

Author Information

  1. Institut für Organische Chemie der Technischen Universität Berlin, Straße des 17. Juni 135, D-10623 Berlin Fax: (internat.) + 49(0)30/314-21102

Publication History

  1. Issue published online: 7 DEC 1998
  2. Article first published online: 7 DEC 1998
  3. Manuscript Received: 12 MAY 1998

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Keywords:

  • Ab initio calculations;
  • Mass spectrometry;
  • Gas-phase chemistry;
  • Ammonia oxide;
  • Hydroxylamine

Abstract

Mass-spectrometric experiments were combined with ab initio calculations to explore the cationic and neutral [H3,N,O]☆+/0 potential energy surfaces and relevant anionic species. The calculations predict the existence of three stable cationic and neutral [H3,N,O]☆+/0 isomers, i.e. ammonia oxide H3NO☆+/0 (1☆+/0), hydroxylamine H2NOH☆+/0 (2☆+/0) and the imine-water complex HNOH2☆+/0 (3☆+/0). Hydroxylamine 2 represents the most stable isomer on the neutral surface (Erel = 0), and the metastable isomers 1 (Erel = 24.8 kcal mol–1) and 3 (Erel = 61.4 kcal mol–1) are separated by barriers of 49.5 kcal mol–1 and 64.2 kcal mol–1, respectively. Adiabatic ionization of 2 (IEa = 9.15 eV) yields 2☆+, which is 21.4 kcal mol–1 more stable than 1☆+ and 36.4 kcal mol–1 more stable than 3☆+. The barriers associated with the isomerizations of the cations are 58.6 kcal mol–1 for 2☆+ → 1☆+ and 71.4 kcal mol–1 for 2☆+ → 3☆+. Collisional activation (CA) and unimolecular decomposition (MI) experiments allow for a clear distinction of 1☆+ from 2☆+. Besides, neutralization/reionization (NR) experiments strongly support the gas-phase existence of the long-sought neutral ammonia oxide.

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