Gas-phase spectroscopy of the unstable acetonitrile N-oxide molecule, CH3CNO

T. Pasinszki, Nicholas P C Westwood

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

The unstable acetonitrile N-oxide molecule, CH3CNO, has been thermolytically generated in very high yield in the gas phase from its stable ring dimer, dimethylfuroxan, and studied by ultraviolet photoelectron spectroscopy, photoionization mass spectroscopy, and mid-infrared spectroscopy. The individual spectroscopies provide a detailed investigation into the vibrational and electronic character of the molecule, and are supported by both conventional ab initio calculations and density functional theory. The ground-state structure is also investigated by theory at the B3-LYP, MPn (n = 2-4), QCISD, and QCISD(T) levels with medium to large basis sets, and illustrates the need for a precise description of electron correlation. Given that both isomerization and dimerization are feasible loss processes for this unstable molecule, the relative stability of CH3CNO with respect to the known cyanate (CH3OCN), isocyanate (CH3NCO), and fulminate (CH3ONC) isomers and the mechanism of the dimerization processes were studied with density functional theory.

Original languageEnglish
Pages (from-to)1244-1253
Number of pages10
JournalJournal of Physical Chemistry A
Volume105
Issue number8
Publication statusPublished - Mar 1 2001

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Oxides
acetonitrile
Dimerization
Gases
Spectroscopy
vapor phases
dimerization
Molecules
Density functional theory
oxides
Cyanates
Ultraviolet photoelectron spectroscopy
spectroscopy
density functional theory
cyanates
Isocyanates
molecules
Electron correlations
Photoionization
isocyanates

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Gas-phase spectroscopy of the unstable acetonitrile N-oxide molecule, CH3CNO. / Pasinszki, T.; Westwood, Nicholas P C.

In: Journal of Physical Chemistry A, Vol. 105, No. 8, 01.03.2001, p. 1244-1253.

Research output: Contribution to journalArticle

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