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Matrix-isolation and computational study of the HKrCCH...HCCH complex

Knut Willmann, Thomas Vent-Schmidt, Markku Räsänen, Sebastian Riedel, Leonid Khriachtchev – 2015

The HKrCCH⋯HCCH complex is identified in a Kr matrix with the H–Kr stretching bands at 1316.5 and 1305 cm⁻¹. The monomer-to-complex shift of the H–Kr stretching mode is about +60 cm⁻¹, which is significantly larger than that reported previously for the HXeCCH⋯HCCH complex in a Xe matrix (about +25 cm⁻¹). The HKrCCH⋯HCCH complex in a Kr matrix is formed at ∼40 K via the attachment of mobile acetylene molecules to the HKrCCH monomers formed at somewhat lower annealing temperatures upon thermally-induced mobility of H atoms (∼30 K). The same mechanism was previously proposed for the formation of the HXeCCH⋯HCCH complex in a Xe matrix. The assignment of the HKrCCH⋯HCCH complex is fully supported by the quantum chemical calculations. The experimental shift of the H–Kr stretching mode is comparable with the computational predictions (+46.6, +66.0, and +83.2 cm⁻¹ at the B3LYP, MP2, and CCSD(T) levels of theory, respectively), which are also bigger that the calculated shift in the HXeCCH⋯HCCH complex. These results confirm that the complexation effect is bigger for less stable noble-gas hydrides.

Titel
Matrix-isolation and computational study of the HKrCCH...HCCH complex
Verfasser
Knut Willmann, Thomas Vent-Schmidt, Markku Räsänen, Sebastian Riedel, Leonid Khriachtchev
Schlagwörter
Matrix-Isolation Spectroscopy, Krypton, Noble Gas Compounds
Datum
2015
Quelle/n
Erschienen in
RSC Adv. 2015, 5 (45), 35783-35791
Zitierweise
DOI: 10.1039/C5RA01880C
Sprache
eng