Local reactivity of metal overlayers: Density functional theory calculations of Pd on Au

Roudgar, Ata; Groß, Axel

doi:10.1103/physrevb.67.033409

Cited by 144 publications

(137 citation statements)

References 32 publications

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“…The adsorption energies of these two probe atoms on different sections of the Au(111) reconstruction can be used as a probe for the local reactivity 48,49 of the surface, particularly during the formation of covalently coupled molecular nanostructures. Similar to the atomic coordination-driven contrast in catalytic activity between solid gold and the Au nanoparticles, these energies measure both the local coordination and local electronic structure changes across the reconstruction.…”

Section: Surface Electronic Structure and Reactivitymentioning

confidence: 99%

Structure and local reactivity of the Au(111) surface reconstruction

2013

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The close-packed (111) surface of gold is well known to show a 22 × √ 3 reconstruction on single nm lengths with a long-range herringbone pattern on scales of a few hundred nm. Here we investigate the local reconstruction using density functional theory and compare the results to scanning tunneling microscopy experiments. Moreover, we use hydrogen and fluorine as probe atoms to investigate changes in the ability of the Au(111) surface to catalyze the reactions involved in the formation of molecular nanostructures. We find a small variation of the reactivity across different surface sites and link those results to the local coordination environment of the face-centered-cubic (fcc), hexagonal-close-packed (hcp), and ridge regions. Finally, we scrutinize a commonly used approximation in density functional studies, namely that Au (111) is atomically flat and a perfect termination of the fcc lattice.

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Section: Surface Electronic Structure and Reactivitymentioning

confidence: 99%

Structure and local reactivity of the Au(111) surface reconstruction

2013

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“…We will base our analysis on the d-band model which has been used quite successfully to understand trends in adsorption energies from one transition metal to the next [8,[15][16][17][18][19]. According to the d-band model, it is useful to think of the formation of the adsorbate-surface bond as taking place in two steps.…”

Section: Scaling Properties Of Adsorption Energies For Hydrogen-contamentioning

confidence: 99%

Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces

et al. 2007

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“…For the transition-metal surfaces, the scaling relationships can be understood within the d-band model. [34][35][36][37][38][39] The variation in adsorption energies for a given atom or molecule among the transition metals is mainly given by the variations in the strength of the coupling of the valence states of the adsorbate with the d states of the transition metal. The variations in the adsorption energy of an atom A from one transition-metal surface to the next reflect this.…”

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confidence: 99%

Scaling Relationships for Adsorption Energies on Transition Metal Oxide, Sulfide, and Nitride Surfaces

et al. 2008

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There has been substantial progress in the description of adsorption and chemical reactions of simple molecules on transition-metal surfaces. Adsorption energies and activation energies have been obtained for a number of systems, and complete catalytic reactions have been described in some detail. [1][2][3][4][5][6][7] Considerable progress has also been made in the theoretical description of the interaction of molecules with transition-metal oxides, [8][9][10][11][12][13][14][15][16][17][18][19] sulfides, [20][21][22][23][24][25] and nitrides, [26][27][28][29] but it is considerably more complicated to describe such complex systems theoretically. Complications arise from difficulties in describing the stoichiometry and structure of such surfaces, and from possible shortcomings in the use of ordinary generalized gradient approximation (GGA) type density functional theory (DFT).[30]Herein we introduce a method that may facilitate the description of the bonding of gas molecules to transitionmetal oxides, sulfides, and nitrides. It was recently found that there are a set of scaling relationhips between the adsorption energies of different partially hydrogenated intermediates on transition-metal surfaces.[31] We will show that similar scaling relationships exist for adsorption on transition metal oxide, sulfide, and nitride surfaces. This means that knowing the adsorption energy for one transition-metal complex will make it possible to quite easily generate data for a number of other complexes, and in this way obtain reactivity trends.The results presented herein have been calculated using self-consistent DFT. Exchange and correlation effects are described using the revised Perdew-Burke-Ernzerhof (RPBE) [32] GGA functional. It is known that GGA functionals give adsorption energies with reasonable accuracy for transition metals. [32,33] It is not clear, however, whether a similar accuracy can be expected for the oxides, sulfides, and nitrides, although there are examples of excellent agreement between DFT calculations and experiments, for example, with RuO 2 surfaces.[9] In our study we focused entirely on variations in the adsorption energies from one system to another, and we expected that such results would be less dependent than the absolute adsorption energies on the description of exchange and correlation.For the nitrides, a clean surface and a surface with a nitrogen vacancy were studied. For MX 2 -type oxides or sulfides, an oxygen-or sulfur-covered surface with an oxygen or sulfur vacancy was studied. The structures of the clean surface considered in the present work and their unit cells are shown in Figure 1. The adsorption energies given below are for the adsorbed species in the most stable adsorption site on the surface.By performing calculations for a large number of transition-metal surfaces of different orientations, [31] it was found that the adsorption energy of intermediates of the type AH x is linearly correlated with the adsorption energy of atom A (N, O, S) according to Equation (1):Here the scali...

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Local reactivity of metal overlayers: Density functional theory calculations of Pd on Au

Cited by 144 publications

References 32 publications

Structure and local reactivity of the Au(111) surface reconstruction

Structure and local reactivity of the Au(111) surface reconstruction

Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces

Scaling Relationships for Adsorption Energies on Transition Metal Oxide, Sulfide, and Nitride Surfaces

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