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Issue 35, 2017
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Characterization of the HCN⋯CO complex and its radiation-induced transformation to HNC⋯CO in cold media: an experimental and theoretical investigation

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Abstract

The HCN⋯CO complex and its X-ray induced transformation to HNC⋯CO in solid noble gas (Ng) matrices (Ng = Ne, Ar, Kr, Xe) was first characterized by matrix isolation FTIR spectroscopy at 5 K. The HCN⋯CO complex was obtained by deposition of HCN/CO/Ng gaseous mixtures. The assignment was based on extensive quantum chemical calculations at the CCSD(T) level of theory. The calculations predicted two computationally stable structures for HCN⋯CO and three stable structures for HNC⋯CO. However, only the most energetically favorable linear structures corresponding to the co-ordination between the H atom of HCN (HNC) and the C atom of CO have been found experimentally. The HCN⋯CO complex demonstrates a considerable red shift of the H–C stretching vibrations (−24 to −38 cm−1, depending on the matrix) and a blue shift of the HCN bending vibrations (+29 to +32 cm−1) with respect to that of the HCN monomer, while the C[double bond, length as m-dash]O stretching mode is blue-shifted by 15 to 20 cm−1 as compared to the CO monomer. The HNC⋯CO complex reveals a strong red shift of the H–N bending (−77 to −118 cm−1) and a strong blue shift of the HNC bending mode (ca. +100 cm−1) as compared to the HNC monomer, whereas the C[double bond, length as m-dash]O stretching is blue-shifted by 24 to 29 cm−1 with respect to that of the CO monomer. The interaction energies were determined to be 1.01 and 1.87 kcal mol−1 for HCN⋯CO and HNC⋯CO, respectively. It was found that the formation of complexes with CO had a remarkable effect on the radiation-induced transformations of HCN. While the dissociation of HCN to H and CN is suppressed in complexes, the isomerization of HCN to HNC is strongly catalyzed by the complexation with CO. The astrochemical implications of the results are discussed.

Graphical abstract: Characterization of the HCN⋯CO complex and its radiation-induced transformation to HNC⋯CO in cold media: an experimental and theoretical investigation

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Publication details

The article was received on 24 May 2017, accepted on 11 Aug 2017 and first published on 15 Aug 2017


Article type: Paper
DOI: 10.1039/C7CP03518G
Citation: Phys. Chem. Chem. Phys., 2017,19, 24348-24356
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    Characterization of the HCN⋯CO complex and its radiation-induced transformation to HNC⋯CO in cold media: an experimental and theoretical investigation

    S. V. Kameneva, D. A. Tyurin and V. I. Feldman, Phys. Chem. Chem. Phys., 2017, 19, 24348
    DOI: 10.1039/C7CP03518G

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