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Insights into the enhanced Ce[triple bond, length as m-dash]N triple bond in the HCe[triple bond, length as m-dash]N molecule.
Physical Chemistry Chemical Physics : PCCP 2017 March 23
Herein, an experimental study of the vibrational spectra of HCeN was carried out in solid argon, followed by theoretical investigations of molecular structures and the nature of Ce[triple bond, length as m-dash]N bond. The absorption band at 937.7 cm-1 with the 1.0311 14 N/15 N isotopic shift ratio is characteristic of Ce[triple bond, length as m-dash]N stretching band for HCeN, showing a 94 cm-1 higher shift relative to that of the diatomic CeN molecule. This large frequency shift indicates a much stronger Ce[triple bond, length as m-dash]N bond in HCeN, which is confirmed by DFT calculations. Qualitative orbital interaction and orbital composition analyses suggest that the addition of the H ligand to the Ce center will activate the 4f valence shell and strengthen the covalent bond between Ce and N, which may contribute to enhance the Ce[triple bond, length as m-dash]N triple bond in the HCeN molecule.
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