J Chem Phys. 2004 Aug 15;121(7):3009-18. doi: 10.1063/1.1768933.

Infrared spectrum and stability of a pi-type hydrogen-bonded complex between the OH and C2H2 reactants.

The Journal of chemical physics

James B Davey, Margaret E Greenslade, Mark D Marshall, Marsha I Lester, Martyn D Wheeler

PMID: 15291610 DOI: 10.1063/1.1768933

Abstract

A hydrogen-bonded complex between the hydroxyl radical and acetylene has been stabilized in the reactant channel well leading to the addition reaction and characterized by infrared action spectroscopy in the OH overtone region. Analysis of the rotational band structure associated with the a-type transition observed at 6885.53(1) cm(-1) (origin) reveals a T-shaped structure with a 3.327(5) A separation between the centers of mass of the monomer constituents. The OH (v = 1) product states populated following vibrational predissociation show that dissociation proceeds by two mechanisms: intramolecular vibrational to rotational energy transfer and intermolecular vibrational energy transfer. The highest observed OH product state establishes an upper limit of 956 cm(-1) for the stability of the pi-type hydrogen-bonded complex. The experimental results are in good accord with the intermolecular distance and well depth at the T-shaped minimum energy configuration obtained from complementary ab initio calculations, which were carried out at the restricted coupled cluster singles, doubles, noniterative triples level of theory with extrapolation to the complete basis set limit.

(c) 2004 American Institute of Physics.

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• Journal Article