The chemisorption of spin polarised NO on Ag{111}

Jigato, Manuel Pérez; King, David A.; Yoshimori, Akira

doi:10.1016/s0009-2614(98)01273-1

Cited by 54 publications

(31 citation statements)

References 21 publications

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“…Such stabilization by forming a dimer was also reported in theoretical calculations elsewhere. 36 Although our results are consistent with the previous work 12 and experimental results, it is well known that isolated ͑gas phase͒ NO dimer is a challenging system for various DFT methods as well as other ab initio approaches. Therefore we check the validity of our DFT-PBE calculation for our purpose and point out its limitations.…”

Section: A Ordered Dimer Structure In the ␦ Phasesupporting

confidence: 92%

“…12 Their results are consistent with ours, i.e., a dimer in a spin-paired configuration, while a monomer has almost the same spin density as the free NO molecule. Therefore we conclude that an adsorbed dimer is chemically "binding" monomers by formation of bonding.…”

Section: A Ordered Dimer Structure In the ␦ Phasesupporting

confidence: 89%

“…10,11 Spin-density analysis by density functional theory ͑DFT͒ calculations supports the chemisorption of a dimer. 12 Recently, from clear scanning tunneling microscopy ͑STM͒ images, Carlisle and King observed four different ordered dimer phases, which are named ␣, ␤, , and ␦. The ␦ phase, whose coverage is 0.25 ML, is the most stable.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical study of the photodesorption mechanism of nitric oxide on a Ag(111) surface: A nonequilibrium Green’s function approach to hot-electron tunneling

Nakamura

Yamashita

2006

The Journal of Chemical Physics

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The photoinduced desorption of NO molecules on a Ag surface was studied theoretically using a recently developed method based on the nonequilibrium Green's function approach combined with the density functional theory. Geometry optimizations for the stable NO dimer phase were carried out, and two structures of adsorbed dimers were identified. We calculated the reaction probabilities as a function of incident photon energy for each of the dimers and compared them with experimental action spectra. The two main features of the action spectra, (i) a long tail to the long wavelength (approximately 600 nm) and (ii) a rapid increase at approximately 350 nm, were well reproduced. By theoretical analysis, we found the importance of quantum interference for the interfacial charge transfer between the metal substrate and the adsorbate, as well as the contribution of secondary electrons. Our calculations suggest that the photoactive species is dimeric and that the resonant level is single for the photodesorption of NO.

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Section: A Ordered Dimer Structure In the ␦ Phasesupporting

confidence: 92%

Section: A Ordered Dimer Structure In the ␦ Phasesupporting

confidence: 89%

Section: Introductionmentioning

confidence: 99%

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Theoretical study of the photodesorption mechanism of nitric oxide on a Ag(111) surface: A nonequilibrium Green’s function approach to hot-electron tunneling

Nakamura

Yamashita

2006

The Journal of Chemical Physics

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“…For certain configurations of chemisorbed NO the calculations were repeated enforcing spin polarization without, however, leading to any further stabilization. Growing scientific literature on density functional studies of NO adsorption at metallic surfaces shows the present approach a viable one [6,10,[12][13][14][15][16][17][18][19][20].…”

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confidence: 98%

Bond Activation at Monatomic Steps: NO Dissociation at Corrugated Ru(0001)

1999

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The NO bond activation at a corrugated Ru(0001) surface is investigated using density functional theory. Monatomic steps in the Ru surface are found to offer completely new reaction pathways with highly reduced energy barriers compared to reaction at a flat surface. The calculated energy barriers are found to be dominated by final state effects. The favorable barriers at the step edges result from the attractive chemisorption potential energies of the noninteracting reaction products, atomic N and O, and from a minimal degree of intramolecular repulsion mediated through the substrate. PACS numbers: 82.65.My, 82.20.Kh, 82.30.Lp The modeling of supported catalysts suffers from the socalled structure gap. The mass produced catalysts contain the reactive metal in a highly dispersed state as small particles. These particles are likely to have a large number of steps at their surfaces as well as a high concentration of facet edges between intersecting planes. In the modeling of the catalysts, surface science studies of the reactivity of low index single crystalline surfaces are most often used, despite the fact that the structure of such metal surfaces is different from that of the real catalysts. This is the structure gap [1,2]. Experimental studies have shown that atomic steps are of importance for the overall reactivity of a metal surface [3]. Most prominently, the scanning tunneling microscopy (STM) study by Zambelli et al. [4] revealed that at room temperature, the atomic steps are the only active sites for NO bond activation at surfaces vicinal to Ru(0001). There is, however, still a call for theoretical studies of the reactivity of step edges of metal surfaces in order to understand when and why the steps are of importance for the modeling of catalytic reactions.In the present Letter, the higher reactivity of monatomic steps at Ru(0001) in terms of NO bond activation is demonstrated using density functional theory calculations. The effect of the step edges is dramatic. Energy barriers for NO dissociation at the Ru step edges are found to be up to 1 eV smaller than the value at the flat Ru(0001) surface. The higher ability for bond activation at the step edges is a consequence of a stronger rebonding of the reaction products (i.e., atomic N and O) at the step edges. This becomes apparent when the calculated energy barriers are broken down into two contributions: the rebonding potential energy of noninteracting N and O atoms in the transition state geometry and the interaction energy between the two atoms. The first term is dominant if in the transition state the N and O atoms do not share any immediate nearest neighbor Ru atoms in the surface. The second term, however, becomes progressively more important the more Ru atoms the N and O atoms share in the transition state.The Letter is organized as follows. First the computational setup is introduced. Next, the results for the NO bond activation are given, and finally the analysis is presented.Density functional theory is used for the calculation of total ener...

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“…[53] could either be the result of a direct interaction caused by the overlap of the electronic wave functions of neighbouring NO molecules or due to an indirect interaction mediated by the Pt substrate. As the first type of interaction would most probably favour the formation of chemisorbed (NO) 2 dimers [54], which according to Ref. [18] is not observed in the NO/Pt(111) system, we tend to suggest that the strong vibrational coupling which gives rise to a single vibrational Brought to you by | University of California Authenticated Download Date | 6/2/15 1:49 AM band at θ Ͼ 0.25 originates from a substrate mediated electronic interaction between neighbouring NO molecules.…”

Section: A High-coverage No Adsorption Mechanismmentioning

confidence: 99%

In-Situ Detection of NO Chemisorbed on Platinum Using Infrared-Visible Sum-Frequency Generation (SFG)

Metka¹,

Schweitzer

Volpp³

et al. 2000

Zeitschrift Für Physikalische Chemie

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NO Adsorption / Catalysis / Sum-Frequency Generation / Low-Energy Electron DiffractionIn-situ sum-frequency generation (SFG) surface vibrational spectroscopy for different polarisation arrangements has been employed along with low-energy electron diffraction (LEED) measurements and kinetic modelling calculations to study NO adsorption on Pt(111) as a function of NO gas-phase pressure (p NO ϭ 10 Ϫ9 Ϫ10 Ϫ4 mbar) and substrate temperature (T s ϭ 300Ϫ400 K). The observation of a NO stretching vibrational band with a frequency of 1724 cm Ϫ1 with different signal intensities for ssp and ppp polarisation combinations indicated the presence of tilted NO species at high NO coverages (θ Ն 0.5). At lower coverages (0.5 Ͼ θ Ͼ 0.25) the adsorption geometry was found to change towards upright NO giving rise to a vibrational band with slightly lower frequencies of 1716Ϫ1720 cm Ϫ1 . LEED studies demonstrated that under adsorption/desorption equilibrium conditions up to saturation coverage NO adsorption leads to the formation of ordered adsorbate structures with 2ϫ 2 periodicity. The detailed analysis of the pressure and temperature dependence of the LEED and SFG surface vibrational data is consistent with a NO adsorption mechanism involving the successive formation of Pt(111)ϩp(2ϫ2)-NO (θ ϭ 0.25), Pt(111)ϩ(2ϫ2)-2 NO (θ ϭ 0.5) and Pt(111)ϩ(2ϫ2)-3 NO (θ ϭ 0.75) adsorbate structures as the NO pressure is increased from 10 Ϫ9 to 10 Ϫ4 mbar. A tentative binding site assignment for the two higher-coverage structures with θ ϭ 0.5 and 0.75 is proposed and discussed in the light of the present and previous experimental data.

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The chemisorption of spin polarised NO on Ag{111}

Cited by 54 publications

References 21 publications

Theoretical study of the photodesorption mechanism of nitric oxide on a Ag(111) surface: A nonequilibrium Green’s function approach to hot-electron tunneling

Theoretical study of the photodesorption mechanism of nitric oxide on a Ag(111) surface: A nonequilibrium Green’s function approach to hot-electron tunneling

Bond Activation at Monatomic Steps: NO Dissociation at Corrugated Ru(0001)

In-Situ Detection of NO Chemisorbed on Platinum Using Infrared-Visible Sum-Frequency Generation (SFG)

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