DOI: 10.1002/qua.560420504. Molecular orbital cluster model study of bonding and vibrations of CO adsorbed on MgO surface

Molecular orbital cluster model study of bonding and vibrations of CO adsorbed on MgO surface

10.1002/qua.560420504

Crossref journal-article

Wiley

International Journal of Quantum Chemistry (311)

Abstract

AbstractThe interaction of CO with the MgO(100) surface has been investigated by means of all electron cluster model calculations. The CO molecule is bound on the Mg2+ site of MgO with a chemisorption energy of about 0.2 eV. The binding mechanism is electrostatic in nature and arises almost entirely from the interaction of the weak electric field generated by the ionic surface and the CO charge distribution, with negligible contributions from chemical effects as the CO σ donation. When CO is bound through carbon, its vibrational frequency increases with respect to the gas‐phase value. This shift, Δ, has been analyzed and decomposed into the sum of different contributions. It is found that the positive Δω does not arise entirely from the field–dipole interaction but is due, in part, to the increase in Pauli repulsion occurring when the CO molecule vibrates in the presence of the surface “wall.” A stronger electrostatic interaction, bringing the CO adsorbate closer to the surface, increases this wall effect and results in a more pronounced positive ω shift. It is also found that the two CO orientations exhibit opposite shifts in ωe, thus, the two orientations can be distinguished, in principle, by IR spectroscopy. The analysis of our ab initio cluster wave functions gives a very different picture than the standard view of the metal–CO bond as arising from σ donation and π back donation.

Bibliography

Pacchioni, G., Cogliandro, G., & Bagus, P. S. (1992). Molecular orbital cluster model study of bonding and vibrations of CO adsorbed on MgO surface. International Journal of Quantum Chemistry, 42(5), 1115â1139. Portico.

Authors 3

Gianfranco Pacchioni (first)
Giuseppe Cogliandro (additional)
Paul S. Bagus (additional)

References 40 Referenced 220

10.1007/978-3-642-73887-6
{'key': 'e_1_2_1_3_2', 'volume-title': 'Infrared Spectroscopy of Adsorbed Species', 'author': 'Little L. H.', 'year': '1966'} / Infrared Spectroscopy of Adsorbed Species by Little L. H. (1966)
{'key': 'e_1_2_1_4_2', 'volume-title': 'Infrared Spectroscopy in Surface Chemistry', 'author': 'Hair M. L.', 'year': '1967'} / Infrared Spectroscopy in Surface Chemistry by Hair M. L. (1967)
10.1016/S0584-8539(87)80030-2
10.1016/0021-9517(89)90162-0
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F. B.van Duijeneveldt IBM Res. Report RJ 945 1971(unpublished).
{'key': 'e_1_2_1_15_2', 'volume-title': 'Tables of Interatomic Distances and Configuration in Molecules and Ions', 'year': '1958'} / Tables of Interatomic Distances and Configuration in Molecules and Ions (1958)
10.1016/0301-0104(85)80075-6
10.1007/BF02394557
10.1080/00268977800100581
{'key': 'e_1_2_1_17_4', 'volume-title': 'Proceedings of the Workshop on Quantum Chemistry and Molecular Physics', 'author': 'Buenker R. J.', 'year': '1980'} / Proceedings of the Workshop on Quantum Chemistry and Molecular Physics by Buenker R. J. (1980)
10.1016/0166-1280(85)80172-X
10.1021/ja00189a019
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{'key': 'e_1_2_1_23_2', 'volume-title': 'Molecular Spectra and Molecular Structure', 'author': 'Herzberg G.', 'year': '1950'} / Molecular Spectra and Molecular Structure by Herzberg G. (1950)
10.1016/0009-2614(85)85189-7
10.1103/PhysRevB.40.6003
{'key': 'e_1_2_1_26_2', 'first-page': '475', 'volume-title': 'Quantum Chemistry: Basic Aspects, Actual Trends', 'author': 'Bagus P. S.', 'year': '1989'} / Quantum Chemistry: Basic Aspects, Actual Trends by Bagus P. S. (1989)
10.1515/zpch-1982-01140
10.1016/0039-6028(91)90691-K
If all quantities are expressed in a.u. assuming a Mg‐C distance of 4.90 bohr andQ= +2 the corresponding value ofFis about 0.08 a.u. = 4 × 108V/cm. This field is very large; for comparison in an electrochemical cell when a potential of 1 V is applied the electric field is about 5 × 107V/cm.
10.1007/978-1-4615-8600-5

Dates

Type	When
Created	20 years, 7 months ago (Dec. 28, 2004, 4:08 a.m.)
Deposited	1 year, 10 months ago (Sept. 25, 2023, 10:31 a.m.)
Indexed	9 hours, 43 minutes ago (Aug. 21, 2025, 2:29 p.m.)
Issued	33 years, 2 months ago (June 5, 1992)
Published	33 years, 2 months ago (June 5, 1992)
Published Online	20 years, 10 months ago (Oct. 19, 2004)
Published Print	33 years, 2 months ago (June 5, 1992)

Funders 0

None

BibTeX

@article{Pacchioni_1992, title={Molecular orbital cluster model study of bonding and vibrations of CO adsorbed on MgO surface}, volume={42}, ISSN={1097-461X}, url={http://dx.doi.org/10.1002/qua.560420504}, DOI={10.1002/qua.560420504}, number={5}, journal={International Journal of Quantum Chemistry}, publisher={Wiley}, author={Pacchioni, Gianfranco and Cogliandro, Giuseppe and Bagus, Paul S.}, year={1992}, month=jun, pages={1115–1139} }

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