A model for the coadsorption of ions

Newmark, Andrea R.; Schmickler, Wolfgang

doi:10.1016/0022-0728(92)80214-o

Cited by 8 publications

(5 citation statements)

References 9 publications

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“…eq 6.16a). Following refs and , we take Δ s as 1.0 eV. For the chemisorption at the M−V interface, only one self-consistent value of 〈 n s σ 〉 equal to 0.49 is obtained.…”

Section: Numerical Results and Discussionmentioning

confidence: 99%

“…eqs 4.3 and 4.4): The last integral in the above expression diverges, and its lower limit needs a cutoff for obtaining a finite result. This energy cutoff is put at ε Γ , the bottom of conduction band in the metal …”

Section: Electrochemisorption: a Simple Model For Numerical Calculationsmentioning

confidence: 99%

“…This energy cutoff is put at Γ , the bottom of conduction band in the metal. 18 Thus, in the wide-band limit, the interaction energy expression (6.13) gets replaced by In the following sections, the details of the electronic structure of an copper layer adsorbed on gold electrode are considered. We give the results both for the general analysis and the wideband approximation.…”

Section: Electrochemisorption: a Simple Model For Numerical Calculationsmentioning

confidence: 99%

“…Herein, a part of adsorbate's self-energy arising due to the metal−adsorbate hybridization is approximated as an energy independent quantity i Δ. This approximation leads to a logarithmic divergence in the energy calculation and necessitates an introduction of a lower cutoff parameter in order to arrive at a finite result . Within the wide-band approximation, the adsorbate Green's function has a single pole structure (Lorentzian density of states) when the intraadsorbate Coulomb repulsion is treated using the Hartree−Fock approximation.…”

Section: Introductionmentioning

confidence: 99%

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Electronic Structure of a Chemisorbed Layer at Electrochemical Interface: Copper Layer on Gold Electrode

Mishra

1999

J. Phys. Chem. B

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Though the importance of chemisorption at the electrochemical interface is well recognized, an electronic level description for the same still remains in a nascent stage. The present work specifically addresses this problem. An appropriate model Hamiltonian based formalism is proposed for a random adsorbate layer with arbitrary coverage and the ensuing twodimensional band formation by metallic adsorbates in the monolayer regime. The coherent potential approximation is employed to handle the randomness. The adsorbate self-energy is evaluated explicitly using the density of states for the substrate band. This takes us beyond the conventional wide-band approximation and removes the logarithmic divergence associated with the binding energy calculations. The formalism is applied to the electrosorption of copper ion on gold electrode, and the coverage dependence of adsorbate charge, binding energy, and adsorbate density of states are determined. The analysis predicts a unique charge configuration of copper adsorbate, having a net positive charge, in the high-coverage regime, and multiple charge states when the coverage is low. Though one of the charge configurations of copper is nearly neutral at small coverage, its positive charge state is the most stable in the entire coverage range. The transition from the relative neutral state of copper at low coverage to a positive charge configuration occurs sharply at the intermediate-coverage region.This transition is caused due to the progressive desolvation of copper adion with increasing coverage. The energy calculations show that copper s-orbital bonding contributes maximally towards the binding energy at the metal-vacuum interface, whereas it is the copper d-orbital bonding which makes chemisorption feasible at the gold electrode. Finally, our numerical results are compared with the relevant experimental studies.

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“…eq 6.16a). Following refs and , we take Δ s as 1.0 eV. For the chemisorption at the M−V interface, only one self-consistent value of 〈 n s σ 〉 equal to 0.49 is obtained.…”

Section: Numerical Results and Discussionmentioning

confidence: 99%

Section: Electrochemisorption: a Simple Model For Numerical Calculationsmentioning

confidence: 99%

Section: Electrochemisorption: a Simple Model For Numerical Calculationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Electronic Structure of a Chemisorbed Layer at Electrochemical Interface: Copper Layer on Gold Electrode

Mishra

1999

J. Phys. Chem. B

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show abstract

“…Since this time, great progress has been made in this area. The Monte Carlo (MC) method as well as Molecular Dynamics (MD) have been successfully used in the last decade for the investigation of the properties of the metal-water [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] and the metal-ionic solution interface [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31]. A strategy commonly used for the description of interactions between all species involved in the simulated process, is to model them by some simple analytical functions derived from the results of quantum calculations.…”

Section: Introductionmentioning

confidence: 99%