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High-Resolution Rovibrational Spectroscopy of Carbon Monoxide Isotopologues Isolated in Solid Parahydrogen Mario E. Fajardo* Air Force Research Laboratory, Munitions Directorate, Ordnance Division, Energetic Materials Branch, AFRL/RWME, 2306 Perimeter Road, Eglin Air Force Base, Florida 32542-5910, United States
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Cite this: J. Phys. Chem. A 117, 50, 13504-13512
J. Phys. Chem. A, 2013, 117 (50), pp 13504–13512 DOI: 10.1021/jp407267u Publication Date (Web): September 26, 2013 Copyright This article not subject to U.S. Copyright. Published 2013 by the American Chemical Society *E-mail:
[email protected].
This article is part of the Terry A. Miller Festschrift special issue.
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We report high-resolution infrared absorption spectra of six different CO isotopologues isolated in cryogenic parahydrogen (pH2) solids. These data provide a stringent test for theories of
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nearly free molecular rotors in crystalline solids, such as crystal field theory, rotation–translation coupling theory, and the pseudorotating cage model. A gas-phase molecule rotates about its center-of-mass (C.M.); a trapped molecule instead rotates about its “center of interaction” (C.I.)
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with the trapping cage, which may differ from the C.M. for heteronuclear diatomics like CO. Isotopic manipulation of CO allows the systematic variation of the C.M. relative to the C.I. We
Received 22 July 2013 Published online 26 September 2013 Published in print 19 December 2013
report remarkably good straight line correlation plots between the observed matrix effects and C.M. locations. Extrapolation of these lines to the limit of vanishing matrix effects yields an “experimental prediction” of the C.I. in excellent (fortuitous?) agreement with the C.I. calculated
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using a linear pH2–CO–pH2 toy model.
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