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Experimental characterization of the weakly anisotropic CN X-2 Sigma(+) + Ne potential from IR-UV double resonance studies of the CN-Ne complex

Beames, Joseph, O'Donnell, Bridget A., Ting, Melodie, Lester, Marsha I. and Stephenson, Thomas A. 2011. Experimental characterization of the weakly anisotropic CN X-2 Sigma(+) + Ne potential from IR-UV double resonance studies of the CN-Ne complex. Journal of Chemical Physics 134 (18) , 184308. 10.1063/1.3586810

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Abstract

IR-UV double resonance spectroscopy has been used to characterize hindered internal rotor states (n K = 00, 11, and 10) of the CN-Ne complex in its ground electronic state with various degrees of CN stretch (νCN) excitation. Rotationally resolved infrared overtone spectra of the CN-Ne complex exhibit perturbations arising from Coriolis coupling between the closely spaced hindered rotor states (11 and 10) with two quanta of CN stretch (νCN = 2). A deperturbation analysis is used to obtain accurate rotational constants and associated average CN center-of-mass to Ne separation distances as well as the coupling strength. The energetic ordering and spacings of the hindered internal rotor states provide a direct reflection of the weakly anisotropic intermolecular potential between CN X 2Σ+ and Ne, with only an 8 cm−1 barrier to CN internal rotation, from which radially averaged anisotropy parameters (V 10 and V 20) are extracted that are consistent for νCN = 0-3. Complementary ab initio calculation of the CN X 2Σ+ + Ne potential using MRCI+Q extrapolated to the complete one-electron basis set limit is compared with the experimentally derived anisotropy by optimizing the radial potential at each angle. Experiment and theory are in excellent accord, both indicating a bent minimum energy configuration and nearly free rotor behavior. Analogous experimental and theoretical studies of the CN-Ne complex upon electronic excitation to the CN B 2Σ+ state indicate a slightly more anisotropic potential with a linear CN-Ne minimum energy configuration. The results from these IR-UV double resonance studies are compared with prior electronic spectroscopy and theoretical studies of the CN-Ne system.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Institute of Physics
ISSN: 0021-9606
Last Modified: 04 Jun 2017 08:06
URI: http://orca-mwe.cf.ac.uk/id/eprint/72862

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