Theory of Adsorption on Metal Substrates

Scheffler, Matthias; Stampfl, Catherine

doi:10.1016/s1573-4331(00)80009-8

Cited by 78 publications

(108 citation statements)

References 143 publications

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“…In a large number of cases, DFT calculations agree well with experiments. 25 We have also found that the results of PW91 DFT and those of B3LYP agree well with the CCSD͑T͒ results for H adsorbed on Au clusters. 30 Moreover, B3LYP calculations in Michael Bowers's group 31 agree well with the binding energies of oxygen to small positive Ag clusters.…”

Section: Discussionsupporting

confidence: 78%

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The interaction of oxygen with small gold clusters

Varganov

Olson

Gordon

et al. 2003

The Journal of Chemical Physics

127

118

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Presented in this work are the results of a quantum chemical study of oxygen adsorption on small Aun and Au−n (n=2,3) clusters. Density functional theory(DFT), second order perturbation theory (MP2), and singles and doubles coupled clustertheory with perturbative triples [CCSD(T)] methods have been used to determine the geometry and the binding energy of oxygen to Aun. The multireference character of the wave functions has been studied using the complete active space self-consistent field method. There is considerable disagreement between the oxygen binding energies provided by CCSD(T) calculations and those obtained with DFT. The disagreement is often qualitative, with DFT predicting strong bonds where CCSD(T) predicts no bonds or structures that are bonded but have energies that exceed those of the separated components. The CCSD(T) results are consistent with experimental measurements, while DFT calculations show, at best, a qualitative agreement. Finally, the lack of a regular pattern in the size and the sign of the errors [as compared to CCSD(T)] is a disappointing feature of the DFT results for the present system: it is not possible to give a simple rule for correcting the DFT predictions (e.g., a useful rule would be that DFT predicts stronger binding of O2 by about 0.3 eV). It is likely that the errors in DFT appear not because of gold, but because oxygen binding to a metal cluster is a particularly difficult problem. Presented in this work are the results of a quantum chemical study of oxygen adsorption on small Au n and Au n Ϫ (nϭ2,3) clusters. Density functional theory ͑DFT͒, second order perturbation theory ͑MP2͒, and singles and doubles coupled cluster theory with perturbative triples ͓CCSD͑T͔͒ methods have been used to determine the geometry and the binding energy of oxygen to Au n . The multireference character of the wave functions has been studied using the complete active space self-consistent field method. There is considerable disagreement between the oxygen binding energies provided by CCSD͑T͒ calculations and those obtained with DFT. The disagreement is often qualitative, with DFT predicting strong bonds where CCSD͑T͒ predicts no bonds or structures that are bonded but have energies that exceed those of the separated components. The CCSD͑T͒ results are consistent with experimental measurements, while DFT calculations show, at best, a qualitative agreement. Finally, the lack of a regular pattern in the size and the sign of the errors ͓as compared to CCSD͑T͔͒ is a disappointing feature of the DFT results for the present system: it is not possible to give a simple rule for correcting the DFT predictions ͑e.g., a useful rule would be that DFT predicts stronger binding of O 2 by about 0.3 eV͒. It is likely that the errors in DFT appear not because of gold, but because oxygen binding to a metal cluster is a particularly difficult problem.

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Section: Discussionsupporting

confidence: 78%

“…This is not entirely surprising, since it has been noted frequently that DFT tends to ''overbind.'' 25 If this error were systematic, one could ''correct'' for it and bring the results closer to reality. Unfortunately, as discussed in the following, the errors do not appear to be systematic overbinding.…”

mentioning

confidence: 99%

The interaction of oxygen with small gold clusters

Varganov

Olson

Gordon

et al. 2003

The Journal of Chemical Physics

127

118

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“…24 Another way of tackling the complex problem of the evolution of the geometry and conductance of stretched nanowires is to reduce the level of complexity in description of the atomic structure of the system and to use DFT methodology, but based on jellium models for the nanowire material. Despite its apparent simplicity, such an approach can often capture the main physics of the process at hand, as has been proven with many studies of metal nanostructures and metal surfaces, 29 including the representation of electrodes in conductance studies. 30 Among metallic nanowires sodium is the prototype system for the jellium description, allowing one to efficiently explore various structures.…”

Section: Introductionmentioning

confidence: 99%

Clustering and conductance in breakage of sodium nanowires

et al. 2011

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We study the conductance during the elongation and breakage of Na nanowires described with the ultimate jellium model. A combined approach is used where the nanowire breakage is simulated self-consistently within the density-functional theory, and the wave packet propagation technique is applied for ballistic electron transport. For certain conditions the breakage of the nanowire is preceded by formation of clusters of magic size in the break junction. This affects the conductance G, in particular the shape of the G = 3G 0 to G = G 0 (=2e 2 /h) step upon elongation. The observed trends can be explained as due to the transient trapping of ballistic electrons inside the cluster, leading to a resonant character of the electron transport through the break junction. The cluster-derived resonances appear as peak structures in the differential conductance which may serve as an experimental signature of clustering.

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“…Such a region of electron depletion above the halogen adatom is clearly visible in the electron density contour plots of Ref. 39 shown for Cl adatoms on metal surfaces, although this detail was not mentioned by the authors themselves. As shown in these plots, a positive image charge resides directly beneath the negatively charged halogen adatom.…”

Section: Discussionmentioning

confidence: 92%

Internal electronic structure of adatoms on Fe(110) and Fe(100) surfaces: A low-energyLi+scattering study

2004

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The neutralization of 400-3000 eV 7 Li ϩ ions scattered from clean and adsorbate-covered Fe͑110͒ and Fe͑100͒ surfaces was measured with time-of-flight spectroscopy. Li singly scattered from bromine, iodine, and cesium adatoms has a consistently larger neutral fraction than that for scattered from substrate sites. This suggests that the local electrostatic potential directly above these adatoms is reduced from that of the clean substrate. The neutral fraction of Li scattered from halogen adatoms is surprising in that it decreases as the emission angle moves off-normal, yet increases in the usual manner for cesium and silver adatoms. This indicates that the charge distribution associated with a halogen adsorbate is nonuniform, most likely due to internal polarization. A semiquantitative theoretical analysis shows that a nonuniform internal electron density would give rise to the observed behavior. The polarization of halogen adatoms is likely responsible for anomalous work function changes observed previously. Alkali-ion scattering is shown to be an effective tool for detecting the internal electronic structure of an adatom.

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Theory of Adsorption on Metal Substrates

Cited by 78 publications

References 143 publications

The interaction of oxygen with small gold clusters

The interaction of oxygen with small gold clusters

Clustering and conductance in breakage of sodium nanowires

Internal electronic structure of adatoms on Fe(110) and Fe(100) surfaces: A low-energyLi+scattering study

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