Application of molecular symmetry in near-edge x-ray-absorption spectroscopy of adsorbed species

Somers, J.; Robinson, A. W.; Lindner, Th.; Ricken, D. E.; Bradshaw, Alexander M.

doi:10.1103/physrevb.40.2053

Cited by 65 publications

(26 citation statements)

References 43 publications

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“…This order agrees with previous theoretical analysis [24] . In Table 1 [25][26][27] and the previous calculated results [24,28] for O-Cu distance. Here, the experimental formate adsorption energy was calculated from the difference in the activation energy between formate synthesis and formate decomposition [29] .…”

Section: The Preferred Adsorption Form Of Formate On Copper Metalmentioning

confidence: 93%

“…The surface extended X-ray absorption fine structure (SEXAFS), near-edge X-ray absorption fine structure (NEXAFS) and photoelectron diffraction (PhD) results show that formate is oriented with its molecular plane normal to the metal surfaces, and the short-bridge site is the most stable adsorption site on Cu(110) and Cu(100) surfaces [11][12][13] . The oxygen atoms of formate are located at almost the same distance from the surface with a Cu-O nearest-neighbor distance of 1.98 ± 0.04 Å [11][12][13] . On the Cu (111) surface, normal incidence X-ray standing wavefiled absorption (NIXSW) results show that oxygen atoms of formate are located at atop sites, and the distance between oxygen atoms and nearest-neighboring copper atoms is 1.92 ± 0.04 Å [14] .…”

Section: Introductionmentioning

confidence: 98%

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The relationship between formate adsorption energy and electronic properties: A first principles density functional theory study

Wang

Morikawa

Nakamura

2009

Sci. China Ser. B-Chem.

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First principles density functional theory calculations have been performed for the chemisorption of formate adsorption on some metal surfaces. For the most stable adsorption site of short-bridge, the calculated formate adsorption energy follows the order of Au(110) < Ag(110) < Cu(110) < Pd(110) < Pt(110) < Ni(110) < Rh(110) < Fe(100) < Mo(100), and a clear linear correlation exists between the adsorption energy and the corresponding heat of formation of metal oxides. Moreover, it has been found that the formate adsorption energy for the transition metals can be correlated well with its d-band center (ε d ), and the IB Group metals can be described by the coupling matrix element square (V ad 2 ).formate, metal, DFT-GGA, slab model, adsorption energy, d-band center

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Section: The Preferred Adsorption Form Of Formate On Copper Metalmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 98%

The relationship between formate adsorption energy and electronic properties: A first principles density functional theory study

Wang

Morikawa

Nakamura

2009

Sci. China Ser. B-Chem.

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“…The effect of reduced symmetry caused by interaction with the surface, as postulated by Somers et at. [3], will be clearly demonstrated for one of these metal-adsorbate resonances.The theoretical results presented were obtained from first principles using a combination of ab initio cluster calculations and Stieltjes moment theory analysis. Generalized valence-bond (GVB) and configuration-interaction calculations were first used to determine the ground-state geometry for C2 adsorbed in the long bridge site on Ag(llO) using a 24-atom cluster model [4].…”

mentioning

confidence: 88%

Chemisorption-Induced Changes in the X-Ray-Absorption Fine Structure of Adsorbed Species

et al. 1991

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Experimental and ab initio theoretical near-edge x-ray-absorption fine-structure (NEXAFS) spectra of Cz/Agd 10) are presented. The results show that chemisorption can strongly affect the NEXAFS of a molecular species. From examination of the molecular orbitals associated with the resonance structures of gas phase and adsorbed C2 it is further demonstrated that near-edge spectroscopy can be used to gain information about the mechanism of molecule-substrate interaction.PACS numbers: 78.70.DmIn assigning the resonance features in the near-edge xray-absorption fine-structure (NEXAFS) spectra of an adsorbed molecule, it is often assumed that the near-edge structure of the molecule is qualitatively unaltered by the adsorption process. The assignment of adsorbate spectral features is then made by analogy with corresponding features present in the gas-phase spectrum of the molecule, the so-called "decoupled molecule" approach. So many apparently successful assignments have been made using this approach that it is tempting to conclude that the process of chemisorption has little effect on the nearedge spectrum and that chemisorption-induced features are insignificant [1,2].In this Letter, we discuss the near-edge spectra of a diatomic species, C2, adsorbed on Ag(llO), where the ''decoupled molecule" approach clearly breaks down. We shall show that the experimentally determined spectra are inconsistent with that of gas-phase C2, and that there are chemisorption-induced changes in the spectra which reveal a great deal about the nature of the chemisorptive bond. Moreover, we will demonstrate that some of the features in these spectra are due to metal-adsorbate antibonding interactions, whose presence in near-edge spectra have been generally ignored. The effect of reduced symmetry caused by interaction with the surface, as postulated by Somers et at. [3], will be clearly demonstrated for one of these metal-adsorbate resonances.The theoretical results presented were obtained from first principles using a combination of ab initio cluster calculations and Stieltjes moment theory analysis. Generalized valence-bond (GVB) and configuration-interaction calculations were first used to determine the ground-state geometry for C2 adsorbed in the long bridge site on Ag(llO) using a 24-atom cluster model [4]. A six-Ag-atom cluster model with the same molecular geometry was then used for calculating the improved virtual orbitals (IVOs) of the Hartree-Fock ground-state wave function [5]. Cross sections for the bound-state transitions were obtained from the resulting transition energies and oscillator strengths after broadening with Gaussian functions (FWHM=2.00 eV). For the contin-uum cross section, Stieltjes moment theory techniques were used to find quadrature points for the cumulative oscillator strength distribution from which the photoabsorption cross section was then determined [6]. Similar ab initio calculations have been beneficial in interpreting NEXAFS spectra of gas-phase molecules [6]; this is the first application of the method...

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“…According to the results of IR spectroscopic studies, carboxylic acids, such as formic [41,42], benzoic [43,44] and citric acid [45,46], adsorb on noble metal surface with the carboxylate form. Previous results have shown that the oxygen atoms of the carboxylate groups favorably adsorb on the top sites in a short bridge [47][48][49][50][51]. Furthermore, a bend geometry for the adsorption of R,R-TA molecules on Cu(110) surface has been proposed [12,40,51,52].…”

Section: Ta Adsorption On Cu and Nimentioning

confidence: 97%

Surface Structure of Heterogeneous Catalysts: Cinchona and Tartaric Acid on Solid Surface

Wang

Yan

et al. 2005

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Application of molecular symmetry in near-edge x-ray-absorption spectroscopy of adsorbed species

Cited by 65 publications

References 43 publications

The relationship between formate adsorption energy and electronic properties: A first principles density functional theory study

The relationship between formate adsorption energy and electronic properties: A first principles density functional theory study

Chemisorption-Induced Changes in the X-Ray-Absorption Fine Structure of Adsorbed Species

Surface Structure of Heterogeneous Catalysts: Cinchona and Tartaric Acid on Solid Surface

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