LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

H. Jörg; N. Rösch

doi:10.1016/0039-6028(85)90836-2

LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

H. Jörg, N. Rösch

Professur für Theoretische Chemie (2008 — 2024)

Technische Universität München

Publikation: Beitrag in Fachzeitschrift › Artikel › Begutachtung

9 Zitate (Scopus)

Abstract

The cluster Ni₂CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the NiNi distance fixed at the bulk value. The minimum energy is found at a NiC distance of 1.72 Å and a CO bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm^-1) shows reasonable agreement with EELS data (1810, 1870 cm^-1), whereas the (Ni₂)C frequency of 495 cm^-1 is remarkably higher than the experimental values (380, 400 cm^-1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a₁orbital manifold exhibits strong antibonding effects.

Originalsprache	Englisch
Seiten (von - bis)	L627-L634
Fachzeitschrift	Surface Science
Jahrgang	163
Ausgabenummer	1
DOIs	https://doi.org/10.1016/0039-6028(85)90836-2
Publikationsstatus	Veröffentlicht - 1 Nov. 1985

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10.1016/0039-6028(85)90836-2

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@article{6ba3345ff96341c49a32c188eac1f7eb,

title = "LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces",

abstract = "The cluster Ni2CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the NiNi distance fixed at the bulk value. The minimum energy is found at a NiC distance of 1.72 {\AA} and a CO bond length of 1.19 {\AA}. The vibrational frequency for the CO bond (1850 cm-1) shows reasonable agreement with EELS data (1810, 1870 cm-1), whereas the (Ni2)C frequency of 495 cm-1 is remarkably higher than the experimental values (380, 400 cm-1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a1orbital manifold exhibits strong antibonding effects.",

author = "H. J{\"o}rg and N. R{\"o}sch",

note = "Funding Information: We wish to thank Dr. B.I. Dunlap for providing us with his LCGTO-Xa code and his generous advice. It is a pleasure to acknowledge helpful discussions with Dr. E. Umbach and Professor D. Menzel. N.R. would like to thank Professors J.R. Sabin and M.C. Zerner for their hospitality at the Quantum Theory Project, University of Florida, where this paper was cast into its final form. This work has been supported by the Deutsche Forschungsgemeinschaft.",

year = "1985",

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doi = "10.1016/0039-6028(85)90836-2",

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T1 - LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

AU - Jörg, H.

AU - Rösch, N.

N1 - Funding Information: We wish to thank Dr. B.I. Dunlap for providing us with his LCGTO-Xa code and his generous advice. It is a pleasure to acknowledge helpful discussions with Dr. E. Umbach and Professor D. Menzel. N.R. would like to thank Professors J.R. Sabin and M.C. Zerner for their hospitality at the Quantum Theory Project, University of Florida, where this paper was cast into its final form. This work has been supported by the Deutsche Forschungsgemeinschaft.

PY - 1985/11/1

Y1 - 1985/11/1

N2 - The cluster Ni2CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the NiNi distance fixed at the bulk value. The minimum energy is found at a NiC distance of 1.72 Å and a CO bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm-1) shows reasonable agreement with EELS data (1810, 1870 cm-1), whereas the (Ni2)C frequency of 495 cm-1 is remarkably higher than the experimental values (380, 400 cm-1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a1orbital manifold exhibits strong antibonding effects.

AB - The cluster Ni2CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the NiNi distance fixed at the bulk value. The minimum energy is found at a NiC distance of 1.72 Å and a CO bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm-1) shows reasonable agreement with EELS data (1810, 1870 cm-1), whereas the (Ni2)C frequency of 495 cm-1 is remarkably higher than the experimental values (380, 400 cm-1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a1orbital manifold exhibits strong antibonding effects.

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VL - 163

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JO - Surface Science

JF - Surface Science

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LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

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