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Issue 44, 2009
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Infrared signatures of the NCCO radical

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Abstract

The first definitive infrared signatures of the elusive NCCO radical have been measured using a microwave discharge technique combined with low-temperature matrix-isolation spectroscopy, resulting in a consistent set of vibrational assignments for six isotopologues. The infrared spectra of these NCCO isotopologues were concomitantly established by rigorous variational nuclear-motion computations based on a high-level coupled-cluster quartic vibrational force field [ROCCSD(T)/cc-pCVQZ] and cubic dipole field [ROCCSD/cc-pCVTZ]. Our experimental and theoretical results for NCCO overturn the vibrational assignments in a NIST-JANAF compilation and those from a recent two-dimensional cross-spectral correlation analysis. For the parent isotopologue at 11 K in a nitrogen matrix, we find the signature bands ν2(CO str.) = 1889.2 cm−1 and ν3(CC str.) = 782.0 cm−1. Our variational vibrational computations reveal strong mixing of the ν3 stretching fundamental and the ν4 + ν5 bending combination level for all isotopologues. These Fermi resonances manifest a clear breakdown of the simple normal-mode picture of molecular vibrations at low energies.

Graphical abstract: Infrared signatures of the NCCO radical

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Publication details

The article was received on 29 Jun 2009, accepted on 11 Aug 2009 and first published on 28 Sep 2009


Article type: Paper
DOI: 10.1039/B912803D
Citation: Phys. Chem. Chem. Phys., 2009,11, 10385-10390
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    Infrared signatures of the NCCO radical

    P. R. Schreiner, H. P. Reisenauer, E. Mátyus, A. G. Császár, A. Siddiqi, A. C. Simmonett and W. D. Allen, Phys. Chem. Chem. Phys., 2009, 11, 10385
    DOI: 10.1039/B912803D

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