Adsorbed CO on group 10 metal fragments: A DFT study

Giampaolo Barone, Dario Duca, Sergio Giuffrida

Risultato della ricerca: Article

4 Citazioni (Scopus)

Abstract

DFT calculations on the helicopter and cartwheel rotations of one CO molecule adsorbed at the bridge site on metal-surface fragments, characterized by two (M8) or three (M14) metal-atom layers (M = Ni, Pd, Pt) were performed by the B3LYP[LANL2DZ+6-31 g(d,p)] method, to rationalize the adsorption energetics and the steric hindrance characteristics of surface CO molecules. Potential Energy Surfaces were obtained, either fixing the C-O bond-length or allowing it to change. The behavior of the three metals, as obtained from the study of the configurational space characterizing the CO adsorption on the fragments was explained on the basis of the interaction energies involved in the different CO/M systems. The results, obtained by using the M14 fragments and varying both the C-O and the CO/M distances, point out that the CO adsorption on the Ni fragment is stabilized by surface-configurations in which the O atom is pointing toward a metal center. At variance, C-O bond elongation and stabilization occur on Pd when the O atom is situated between two palladium atoms. The CO adsorption on Pt displays similar characteristics to those observed on the Pd systems, but with the fundamental difference caused by the destabilization of the Pt-O interactions when the O atom is situated exactly between two Pt atoms. The calculations allowed us to estimate the IR spectroscopy frequency and band-broadening of the adsorbed CO stretching by a statistic analysis on a large set of energy ÷ bond-length computed data. Good agreement with the experimental results was obtained for all the metals, in particular concerning the frequencies. Reliable band-broadenings were also obtained for the CO/Ni and CO/Pt systems, while the lower band-broadening value for the CO/Pd system was related to the small extent of the configurational sampling space.
Lingua originaleEnglish
pagine (da-a)1223-1233
Numero di pagine11
RivistaJournal of Chemical Information and Modeling
Volume2009-04-30
Stato di pubblicazionePublished - 2009

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Carbon Monoxide
Discrete Fourier transforms
Metals
Atoms
energy
Adsorption
Group
Bond length
Wire pointing
interaction
stabilization
Potential energy surfaces
Molecules
statistics
Helicopters
Palladium
Stretching
Elongation
Infrared spectroscopy
Stabilization

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Computer Science Applications
  • Library and Information Sciences

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Adsorbed CO on group 10 metal fragments: A DFT study. / Barone, Giampaolo; Duca, Dario; Giuffrida, Sergio.

In: Journal of Chemical Information and Modeling, Vol. 2009-04-30, 2009, pag. 1223-1233.

Risultato della ricerca: Article

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abstract = "DFT calculations on the helicopter and cartwheel rotations of one CO molecule adsorbed at the bridge site on metal-surface fragments, characterized by two (M8) or three (M14) metal-atom layers (M = Ni, Pd, Pt) were performed by the B3LYP[LANL2DZ+6-31 g(d,p)] method, to rationalize the adsorption energetics and the steric hindrance characteristics of surface CO molecules. Potential Energy Surfaces were obtained, either fixing the C-O bond-length or allowing it to change. The behavior of the three metals, as obtained from the study of the configurational space characterizing the CO adsorption on the fragments was explained on the basis of the interaction energies involved in the different CO/M systems. The results, obtained by using the M14 fragments and varying both the C-O and the CO/M distances, point out that the CO adsorption on the Ni fragment is stabilized by surface-configurations in which the O atom is pointing toward a metal center. At variance, C-O bond elongation and stabilization occur on Pd when the O atom is situated between two palladium atoms. The CO adsorption on Pt displays similar characteristics to those observed on the Pd systems, but with the fundamental difference caused by the destabilization of the Pt-O interactions when the O atom is situated exactly between two Pt atoms. The calculations allowed us to estimate the IR spectroscopy frequency and band-broadening of the adsorbed CO stretching by a statistic analysis on a large set of energy ÷ bond-length computed data. Good agreement with the experimental results was obtained for all the metals, in particular concerning the frequencies. Reliable band-broadenings were also obtained for the CO/Ni and CO/Pt systems, while the lower band-broadening value for the CO/Pd system was related to the small extent of the configurational sampling space.",
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T1 - Adsorbed CO on group 10 metal fragments: A DFT study

AU - Barone, Giampaolo

AU - Duca, Dario

AU - Giuffrida, Sergio

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N2 - DFT calculations on the helicopter and cartwheel rotations of one CO molecule adsorbed at the bridge site on metal-surface fragments, characterized by two (M8) or three (M14) metal-atom layers (M = Ni, Pd, Pt) were performed by the B3LYP[LANL2DZ+6-31 g(d,p)] method, to rationalize the adsorption energetics and the steric hindrance characteristics of surface CO molecules. Potential Energy Surfaces were obtained, either fixing the C-O bond-length or allowing it to change. The behavior of the three metals, as obtained from the study of the configurational space characterizing the CO adsorption on the fragments was explained on the basis of the interaction energies involved in the different CO/M systems. The results, obtained by using the M14 fragments and varying both the C-O and the CO/M distances, point out that the CO adsorption on the Ni fragment is stabilized by surface-configurations in which the O atom is pointing toward a metal center. At variance, C-O bond elongation and stabilization occur on Pd when the O atom is situated between two palladium atoms. The CO adsorption on Pt displays similar characteristics to those observed on the Pd systems, but with the fundamental difference caused by the destabilization of the Pt-O interactions when the O atom is situated exactly between two Pt atoms. The calculations allowed us to estimate the IR spectroscopy frequency and band-broadening of the adsorbed CO stretching by a statistic analysis on a large set of energy ÷ bond-length computed data. Good agreement with the experimental results was obtained for all the metals, in particular concerning the frequencies. Reliable band-broadenings were also obtained for the CO/Ni and CO/Pt systems, while the lower band-broadening value for the CO/Pd system was related to the small extent of the configurational sampling space.

AB - DFT calculations on the helicopter and cartwheel rotations of one CO molecule adsorbed at the bridge site on metal-surface fragments, characterized by two (M8) or three (M14) metal-atom layers (M = Ni, Pd, Pt) were performed by the B3LYP[LANL2DZ+6-31 g(d,p)] method, to rationalize the adsorption energetics and the steric hindrance characteristics of surface CO molecules. Potential Energy Surfaces were obtained, either fixing the C-O bond-length or allowing it to change. The behavior of the three metals, as obtained from the study of the configurational space characterizing the CO adsorption on the fragments was explained on the basis of the interaction energies involved in the different CO/M systems. The results, obtained by using the M14 fragments and varying both the C-O and the CO/M distances, point out that the CO adsorption on the Ni fragment is stabilized by surface-configurations in which the O atom is pointing toward a metal center. At variance, C-O bond elongation and stabilization occur on Pd when the O atom is situated between two palladium atoms. The CO adsorption on Pt displays similar characteristics to those observed on the Pd systems, but with the fundamental difference caused by the destabilization of the Pt-O interactions when the O atom is situated exactly between two Pt atoms. The calculations allowed us to estimate the IR spectroscopy frequency and band-broadening of the adsorbed CO stretching by a statistic analysis on a large set of energy ÷ bond-length computed data. Good agreement with the experimental results was obtained for all the metals, in particular concerning the frequencies. Reliable band-broadenings were also obtained for the CO/Ni and CO/Pt systems, while the lower band-broadening value for the CO/Pd system was related to the small extent of the configurational sampling space.

KW - DFT

KW - Infrared spectroscopy

KW - metal surface

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