A density functional study of carbon monoxide adsorption on small cationic, neutral, and anionic gold clusters

Wu, Xueyuan; Senapati, L.; Nayak, Saroj K.; Selloni, Annabella; Hajaligol, Mohammad R.

doi:10.1063/1.1483067

Cited by 207 publications

(237 citation statements)

References 28 publications

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“…45 Moreover, the desorption energies of CO to neutral and charged Au clusters computed with the B3LYP functional are also smaller by 0.4 -0.6 eV than the corresponding values computed with the PW91 functional. 50 However, as mentioned in Ref. 50 the trends of the desorption energies with cluster size are the same with both functionals.…”

Section: Computational Detailsmentioning

confidence: 78%

“…50 However, as mentioned in Ref. 50 the trends of the desorption energies with cluster size are the same with both functionals.…”

Section: Computational Detailsmentioning

confidence: 78%

“…In almost all isomers propene prefers to bind at a corner. This follows the pattern seen for the adsorption of H, 57 CO, 50 O 2 , 23-25,58 methanol, 59 and pyridine 60 on the Au clusters.…”

Section: A the Adsorption Of Propene On Au N "Nä1 -5 8…: Structuresmentioning

confidence: 79%

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Binding of propene on small gold clusters and on Au(111): Simple rules for binding sites and relative binding energies

Chrétien

Gordon

Metiu

2004

The Journal of Chemical Physics

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We use density functional theory(DFT) to investigate the bonding of propene to small gas-phase gold clusters and to a Au(111) surface. The desorption energy trends and the geometry of the binding sites are consistent with the following set of rules.(1) The bond of propene to gold is formed by donation of electron density from the highest occupied molecular orbital (HOMO) of propene to one of the low-lying empty orbitals [denoted by LUMO1, LUMO2, … (LUMO-lowest unoccupied molecular orbital)] of the gold cluster. (2) Propene binds to a site on the Au cluster where one of the low-lying LUMOs protrudes in the vacuum. Different isomers (same cluster, but different binding sites for propene) correspond to sites where different low-lying LUMOs protrude in space. (3) The desorption energy of the lowest energy isomer correlates with the energy of the lowest empty orbital of the cluster; the lower the energy of that LUMO, the higher the desorption energy. (4) If the lowest-lying LUMO protrudes into space at two nonequivalent sites at the edge of a cluster, propene binds more strongly to the site with the lowest coordination. These rules are consistent with the calculated bond energies and geometries for [Aun(C3H6)]q, for n=1−5 and n=8 and q=−1, 0, +1. Based on them we have made a number of predictions that have been confirmed by DFT calculations. The bond of propene to gold is strengthened as the net charge of the cluster varies from −1, to zero, to +1. Compared to a gas-phase cluster, a cluster on a support binds propene more strongly if the support takes electron density from the cluster (e.g., a Au cluster on a goldsurface) and more weakly if the support donates electron density to the cluster (e.g., a Au cluster on an oxygen vacancy on an oxide surface). KeywordsGold, Binding sites, Density functional theory, Desorption, Oxide surfaces Disciplines Chemistry CommentsThe following article appeared in Journal of Chemical Physics 121 (2004) We use density functional theory ͑DFT͒ to investigate the bonding of propene to small gas-phase gold clusters and to a Au͑111͒ surface. The desorption energy trends and the geometry of the binding sites are consistent with the following set of rules. ͑1͒ The bond of propene to gold is formed by donation of electron density from the highest occupied molecular orbital ͑HOMO͒ of propene to one of the low-lying empty orbitals ͓denoted by LUMO1, LUMO2, ... ͑LUMO-lowest unoccupied molecular orbital͔͒ of the gold cluster. ͑2͒ Propene binds to a site on the Au cluster where one of the low-lying LUMOs protrudes in the vacuum. Different isomers ͑same cluster, but different binding sites for propene͒ correspond to sites where different low-lying LUMOs protrude in space. ͑3͒ The desorption energy of the lowest energy isomer correlates with the energy of the lowest empty orbital of the cluster; the lower the energy of that LUMO, the higher the desorption energy. ͑4͒ If the lowest-lying LUMO protrudes into space at two nonequivalent sites at the edge of a cluster, propene binds more strong...

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Section: Computational Detailsmentioning

confidence: 78%

“…50 However, as mentioned in Ref. 50 the trends of the desorption energies with cluster size are the same with both functionals.…”

Section: Computational Detailsmentioning

confidence: 78%

See 1 more Smart Citation

Binding of propene on small gold clusters and on Au(111): Simple rules for binding sites and relative binding energies

Chrétien

Gordon

Metiu

2004

The Journal of Chemical Physics

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“…Related to this, both gas-phase experiments and theory have documented the unusual catalytic activity found for small gold clusters and how this varies with cluster size and charge state. [63][64][65][66][67][68][69][70][71][72][73] The intrinsic reactivity of the pure metal cluster system or its support without the metal is difficult to distinguish with experiments or theory. However, gas phase measurements of isolated metal systems may be able to provide needed insight in this area.…”

Section: Introductionmentioning

confidence: 99%

IR Photodissociation Spectroscopy and Theory of Au⁺(CO)_n Complexes: Nonclassical Carbonyls in the Gas Phase

et al. 2008

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Au+(CO)n complexes are produced in the gas phase via pulsed laser vaporization, expanded in a supersonic jet, and detected with a reflectron time-of-flight mass spectrometer. Complexes up to n = 12 are observed, with mass channels corresponding to the n = 2 and n = 4 showing enhanced intensity. To investigate coordination and structure, individual complexes are mass-selected and probed with infrared photodissociation spectroscopy. Spectra in the carbonyl stretching region are measured for the n = 3−7 species, but no photodissociation is observed for n = 1, 2 due to the strong metal cation-ligand binding. The carbonyl stretch in these systems is blue-shifted 50−100 cm-1 with respect to the free CO vibration (2143 cm-1), providing evidence that these species are so-called "nonclassical" metal carbonyls. Theory at the MP2 and CCSD(T) levels provides structures for these complexes and predicted spectra to compare to the experiment. Excellent agreement is obtained between experiment and theory, establishing that the n = 3 complex is trigonal planar and the n = 4 complex is tetrahedral. Disciplines Chemistry CommentsReprinted (adapted) ReceiVed: NoVember 21, 2007; In Final Form: December 18, 2007 Au + (CO) n complexes are produced in the gas phase via pulsed laser vaporization, expanded in a supersonic jet, and detected with a reflectron time-of-flight mass spectrometer. Complexes up to n ) 12 are observed, with mass channels corresponding to the n ) 2 and n ) 4 showing enhanced intensity. To investigate coordination and structure, individual complexes are mass-selected and probed with infrared photodissociation spectroscopy. Spectra in the carbonyl stretching region are measured for the n ) 3-7 species, but no photodissociation is observed for n ) 1, 2 due to the strong metal cation-ligand binding. The carbonyl stretch in these systems is blue-shifted 50-100 cm -1 with respect to the free CO vibration (2143 cm -1 ), providing evidence that these species are so-called "nonclassical" metal carbonyls. Theory at the MP2 and CCSD(T) levels provides structures for these complexes and predicted spectra to compare to the experiment. Excellent agreement is obtained between experiment and theory, establishing that the n ) 3 complex is trigonal planar and the n ) 4 complex is tetrahedral.

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“…The surface negative charge decreases with the size of the Au clusters. Anionic Au atoms in the cluster have a stronger interaction with O 2 than a neutral Au atom [20,63,[86][87][88][89][90][91][92][93][94][95]. These findings suggest that the active sites for oxygenation on the supported and unsupported Au catalysts [63,93,96] are Au atoms which are negatively charged.…”

Section: Introductionmentioning

confidence: 62%

O2 dissociation in Na-modified gold ultrathin layer on Cu(111)

Politanoa

Chiarello

2010

Gold Bull

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High-resolution electron energy loss spectroscopy has been used to investigate the catalytic properties of Na-doped Au monolayer grown on Cu(111). The presence of Na atoms allows the dissociation of oxygen molecules and the stabilization of atomic oxygen. The strong reduction of the dissociation barrier for O 2 promoted by Na could readily favor many surface chemical reactions, due to the key role of atomic oxygen in many oxidation processes catalyzed by gold.

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A density functional study of carbon monoxide adsorption on small cationic, neutral, and anionic gold clusters

Cited by 207 publications

References 28 publications

Binding of propene on small gold clusters and on Au(111): Simple rules for binding sites and relative binding energies

Binding of propene on small gold clusters and on Au(111): Simple rules for binding sites and relative binding energies

IR Photodissociation Spectroscopy and Theory of Au⁺(CO)_n Complexes: Nonclassical Carbonyls in the Gas Phase

O2 dissociation in Na-modified gold ultrathin layer on Cu(111)

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A density functional study of carbon monoxide adsorption on small cationic, neutral, and anionic gold clusters

Cited by 207 publications

References 28 publications

Binding of propene on small gold clusters and on Au(111): Simple rules for binding sites and relative binding energies

Binding of propene on small gold clusters and on Au(111): Simple rules for binding sites and relative binding energies

IR Photodissociation Spectroscopy and Theory of Au+(CO)n Complexes: Nonclassical Carbonyls in the Gas Phase

O2 dissociation in Na-modified gold ultrathin layer on Cu(111)

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IR Photodissociation Spectroscopy and Theory of Au⁺(CO)_n Complexes: Nonclassical Carbonyls in the Gas Phase