All electron scalar relativistic calculations on adsorption of CO on Pt(111) with full-geometry optimization: a correct estimation for CO site-preference

Orita, Hideo; Itoh, Naotsugu; Inada, Yasuji

doi:10.1016/j.cplett.2003.12.034

Cited by 105 publications

(99 citation statements)

References 26 publications

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“…For instance, LEED experiments report d Pt−C ≃ 1.85Å for atop CO and d Pt−C ≃ 2.08Å for CO at the bridge site and DFT calculations at the GGA level are quite close to these values (see Ref. 39 and references therein). In the substitutional case d Pt−C is quite similar to the on-top case, while the C-O bond is slightly longer than in the other two geometries.…”

Section: Geometry and Energeticsmentioning

confidence: 93%

Interaction of a CO molecule with a Pt monatomic wire: Electronic structure and ballistic conductance

2008

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We carry out a first-principles density functional study of the interaction between a monatomic Pt wire and a CO molecule, comparing the energy of different adsorption configurations (bridge, on top, substitutional, and tilted bridge) and discussing the effects of spin-orbit (SO) coupling on the electronic structure and on the ballistic conductance of two of these systems (bridge and substitutional). We find that, when the wire is unstrained, the bridge configuration is energetically favored, while the substitutional geometry becomes possible only after the breaking of the Pt-Pt bond next to CO. The interaction can be described by a donation/back-donation process similar to that occurring when CO adsorbs on transition-metal surfaces, a picture which remains valid also in presence of SO coupling. The ballistic conductance of the (tipless) nanowire is not much reduced by the adsorption of the molecule on the bridge and on-top sites, but shows a significant drop in the substitutional case. The differences in the electronic structure due to the SO coupling influence the transmission only at energies far away from the Fermi level so that fully-and scalar-relativistic conductances do not differ significantly.

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Section: Geometry and Energeticsmentioning

confidence: 93%

Interaction of a CO molecule with a Pt monatomic wire: Electronic structure and ballistic conductance

2008

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“…5,6,7,8 In all fairness, it must be emphasized that some local basis set codes (specifically DMOL and ADF) seem to give the proper site order for Pt. 9,10 The reason for the discrepancy between local basis set codes and plane wave codes is not yet entirely understood, but it is likely to be related to the different treatment of relativistic effects or basis sets. For Pt, the DMOL code for instance applies effective core potentials to take into account relativistic effects, and the site preference depends critically on the used effective core potential, with the most accurate effective core potential giving the same site preference as plane wave codes.…”

Section: Introductionmentioning

confidence: 99%

CO adsorption on metal surfaces: A hybrid functional study with plane-wave basis set

et al. 2007

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“…The results are also compared to experimental and previous theoretical data on the CO molecule and the CO−Pt complexes to validate how well our calculations estimate the electronic and structural characteristics of these complexes, and also serves as a reference when we discuss the effect of the carbon support on the catalytic activity. Binding of a CO molecule to a metallic surface, in particular Pt, has been studied extensively by a variety of theoretical approaches [56][57][58][59][60] and it is usually discussed using the Dewar-Chatt-Duncanson model. [61][62][63][64] The main characteristics of this model are a charge transfer from the lone-pair (5σ ) orbital of the CO molecule to the 5d orbitals of the Pt atom (σ donation) and a back donation of electron density from the 5d orbitals of the Pt atom to the antibonding 2π * orbitals of the CO molecule, 65 which is in agreement with photoelectron spectroscopy experiments.…”

Section: Co Interaction With Pt Atom and Dimermentioning

confidence: 99%

Influence of Carbon Support on Electronic Structure and Catalytic Activity of Pt Catalysts: Binding to the CO Molecule

2016

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Single-atom catalysts, especially with single Pt atoms, exhibit potentially improved catalytic activity as compared to metal clusters and metal surfaces. Here, the atop and bridged bondings of the CO molecule on the Pt/C system are studied. Vibrational frequencies, Mulliken populations, charge transfer, charge density differences and density of states are examined to determine the influence of the carbon support on electronic properties and catalytic activity of the Pt adatom and dimer. Comparing orbital populations and the amount of electron transfer to/from the CO molecule show that the net amount of electron transfer to the anti-bonding 2π * orbitals of the CO molecule is higher for the supported Pt dimer than for the substrate-free Pt dimer which leads to a lower vibrational frequency and a larger C−O bond distance. The hybridization between the π orbitals of the polycyclic aromatic hydrocarbons surface and the d orbitals of the Pt adatoms is responsible for enhancing the back donation of electrons to the 2π * orbitals of the CO molecule which results in a larger peak below the Fermi level for the 2π * states of the CO molecule in the corresponding density of state analysis. Therefore, it can be concluded that the carbon support significantly enhances the catalytic activity of the Pt atoms in contact with the surface for activating the CO molecule. The calculated C−O vibrational stretching frequencies provide valuable guidance for experiments considering the use of atom-type catalyst as building blocks for designing new catalysts.

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All electron scalar relativistic calculations on adsorption of CO on Pt(111) with full-geometry optimization: a correct estimation for CO site-preference

Cited by 105 publications

References 26 publications

Interaction of a CO molecule with a Pt monatomic wire: Electronic structure and ballistic conductance

Interaction of a CO molecule with a Pt monatomic wire: Electronic structure and ballistic conductance

CO adsorption on metal surfaces: A hybrid functional study with plane-wave basis set

Influence of Carbon Support on Electronic Structure and Catalytic Activity of Pt Catalysts: Binding to the CO Molecule

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