024
Mass-spectrometric experiments together with electronic structure calculations support the existence of the elusive ammonia oxide molecule and its radical cation

M. Br”önstrup, D. Schrö”der, I. Kretzschmar, C. A. Schalley, H. Schwarz – 1998

Mass-spectrometric experiments were combined with ab initio calculations to explore the cationic and neutral [H-3,N,O](.+/0) potential energy surfaces and relevant anionic species. The calculations predict the existence of three stable cationic and neutral [H-3,N,O](.+/0) isomers, i.e, ammonia oxide H3NO.+/0 (1(.+/0)), hydroxylamine HNOH2.+/0 (3(.+/0)) and the imine-water complex HNOH2.+/0 (3(.+/0)). Hydroxylamine 2 represents the most stable isomer on the neutral surface (E-rel = 0), and the metastable isomers 1 (E-rel = 24.8 kcal mol(-1)) and 3 (E-rel = 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 gasphase existence of the long-sought neutral ammonia oxide.

Title
024
Mass-spectrometric experiments together with electronic structure calculations support the existence of the elusive ammonia oxide molecule and its radical cation
Author
M. Br”önstrup, D. Schrö”der, I. Kretzschmar, C. A. Schalley, H. Schwarz
Date
1998-10-01
Identifier
DOI 10.1002/(SICI)1099-0682(199810)1998:10<1529::AID-EJIC1529>3.0.CO;2-Y
Source(s)
Citation
Eur. J. Inorg. Chem. 1998, 1529-1538
Type
Text