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Chemistry

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University of New Hampshire

2004

Articles 1 - 2 of 2

Full-Text Articles in Physical Sciences and Mathematics

Evidence For Partial Quenching Of Orbital Angular Momentum Upon Complex Formation In The Infrared Spectrum Of Oh-Acetylene, Mark D. Marshall, James B. Davey, Margaret E. Greenslade, Marsha I. Lester Jun 2004

Evidence For Partial Quenching Of Orbital Angular Momentum Upon Complex Formation In The Infrared Spectrum Of Oh-Acetylene, Mark D. Marshall, James B. Davey, Margaret E. Greenslade, Marsha I. Lester

Chemistry

The entrance channel leading to the addition reaction between the hydroxyl radical and acetylene has been examined by spectroscopic characterization of the asymmetric CH stretching band of the π-hydrogen bonded OH-acetylene reactant complex. The infrared action spectrum observed at 3278.6 cm−1 (origin) consists of seven peaks of various intensities and widths, and is very different from those previously reported for closed-shell HF/HCl-acetylene complexes. The unusual spectrum arises from a partial quenching of the OH orbital angular momentum in the complex, which in turn is caused by a significant splitting of the OH monomer orbital degeneracy into 2A′ …


Infrared Spectrum And Stability Of A Π-Type Hydrogen-Bonded Complex Between The Oh And C2h2 Reactants, James B. Davey, Margaret E. Greenslade, Mark D. Marshall, Marsha I. Lester, Martyn D. Wheeler May 2004

Infrared Spectrum And Stability Of A Π-Type Hydrogen-Bonded Complex Between The Oh And C2h2 Reactants, James B. Davey, Margaret E. Greenslade, Mark D. Marshall, Marsha I. Lester, Martyn D. Wheeler

Chemistry

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) Å 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 …