A Check of Quantum Chemical Molecular Models of Adsorption on Oxides against Experimental Infrared Data Full article
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Journal of Physical Chemistry (up to 1996)
ISSN: 0022-3654 |
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Output data | Year: 1995, Volume: 99, Number: 41, Pages: 15018-15022 Pages count : 5 DOI: 10.1021/j100041a016 | ||||
Tags | AB-INITIO CALCULATIONS; CARBON-MONOXIDE; METHANOL ADSORPTION; FORCE-CONSTANTS; CLUSTER-MODELS; IONIC-CRYSTALS; ALUMINA GELS; SURFACE; CO; MgO | ||||
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Abstract:
The experimental Δν(CO) and Δν(CN) shifts of CO·X (X = ≡POH, ≡SiOH, ≡SiO(H)Al≡, ≡Al, Mg3c, and Mg4c) and
CD3CN·Y (Y = ≡SiOH, ≡Al, and Mg3c) complexes on oxides are equal within 5 cm-1 to the calculated SCF 6-31G* Δν(CO) and Δν(CN) shifts of their CO·X′ (X′ = OP(OH)3, Si(OH)4, (HO)3SiOHAl-(OH)3, Al(OH)3, Mg4O4, and Mg6O6) and CD3CN·Y′ (Y′ = Si(OH)4, Al(OH)3, and Mg4O4) molecular models. This result allows to conclude that the chemical interactions responsible for these frequency shifts of CO and CD3CN on oxides and in the molecular complexes are nearly identical. It gives strength to the use of the molecular approach for the calculation of intramolecular frequency shifts of probe molecules on oxides. The Δν(CO) shifts of CO on Mg3c and Mg4c sites of magnesium oxide calculated with the Mg4O4 and Mg6O6 molecular models are in significantly better agreement with the experimental data than those obtained using both neutral and charged cluster models of the same size embedded into ±2.0 point-charge Madelung potentials. Hence, in computing the CO frequency shifts on MgO, these simplified embedding procedures worsen the cluster models compared with their "bare" molecular analogs.
Cite:
Pelmenschikov A.G.
, Morosi G.
, Gamba A.
, Coluccia S.
A Check of Quantum Chemical Molecular Models of Adsorption on Oxides against Experimental Infrared Data
Journal of Physical Chemistry (up to 1996). 1995. V.99. N41. P.15018-15022. DOI: 10.1021/j100041a016 WOS Scopus РИНЦ
A Check of Quantum Chemical Molecular Models of Adsorption on Oxides against Experimental Infrared Data
Journal of Physical Chemistry (up to 1996). 1995. V.99. N41. P.15018-15022. DOI: 10.1021/j100041a016 WOS Scopus РИНЦ
Dates:
Submitted: | Nov 10, 1994 |
Accepted: | Jul 10, 1995 |
Published print: | Oct 12, 1995 |
Published online: | May 1, 2002 |
Identifiers:
Web of science | WOS:A1995RZ37300016 |
Scopus | 2-s2.0-0000481048 |
Elibrary | 22579906 |
Chemical Abstracts | 1995:811415 |
Chemical Abstracts (print) | 123:322779 |
OpenAlex | W1984485534 |