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Title: Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O 2 dissociation on Ag(111)

Authors:
;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1258496
Grant/Contract Number:
FG-02-05ER15686
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 23; Related Information: CHORUS Timestamp: 2016-12-26 16:43:21; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Xin, Hongliang, and Linic, Suljo. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O 2 dissociation on Ag(111). United States: N. p., 2016. Web. doi:10.1063/1.4953906.
Xin, Hongliang, & Linic, Suljo. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O 2 dissociation on Ag(111). United States. doi:10.1063/1.4953906.
Xin, Hongliang, and Linic, Suljo. 2016. "Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O 2 dissociation on Ag(111)". United States. doi:10.1063/1.4953906.
@article{osti_1258496,
title = {Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O 2 dissociation on Ag(111)},
author = {Xin, Hongliang and Linic, Suljo},
abstractNote = {},
doi = {10.1063/1.4953906},
journal = {Journal of Chemical Physics},
number = 23,
volume = 144,
place = {United States},
year = 2016,
month = 6
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4953906

Citation Metrics:
Cited by: 1work
Citation information provided by
Web of Science

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  • We have used X-ray absorption spectroscopy and quantum chemical density functional theory calculations to identify critical features in the electronic structure of different sites in alloys that govern the local chemical reactivity. The measurements led to a simple model relating local geometric features of a site in an alloy to its electronic structure and chemical reactivity. The central feature of the model is that the formation of alloys does not lead to significant charge transfer between the constituent metal elements in the alloys, and that the local electronic structure and chemical reactivity can be predicted based on physical characteristics ofmore » constituent metal elements in their unalloyed form.« less
  • Density functional theory calculations were performed to elucidate the underlying physics describing the adsorption energies on doped late transition metal dioxide rutiles. Adsorption energies of atomic oxygen on doped rutiles M{sup D}-M{sup H}O{sub 2}, where transition metal M{sup D} is doped into M{sup H}O{sub 2}, were expressed in terms of a contribution from adsorption on the pure oxide of the dopant M{sup D} and perturbations to this adsorption energy caused by changing its neighboring metal cations and lattice parameters to that of the host oxide M{sup H}O{sub 2}, which we call the ligand and strain effects, respectively. Our analysis ofmore » atom projected density of states revealed that the t{sub 2g}-band center had the strongest correlation with adsorption energies. We show that charge transfer mediated shifts to the t{sub 2g}-band center describe the ligand effect, and the radii of the atomic orbitals of metal cations can predict the magnitude and direction of this charge transfer. Strain produces systematic shifts to all features of the atom projected density of states, but correlations between the strain effect and the electronic structure were dependent on the chemical identity of the metal cation. The slope of these correlations can be related to the idealized d-band filling. This work elucidates the underlying physics describing adsorption on doped late transition metal oxides and establishes a foundation for models that use known chemical properties for the prediction of reactivity.« less
  • Cited by 5
  • While it is fairly straightforward to predict the relative chemical reactivity of pure metals, obtaining similar structure-performance relationships for alloys is more challenging. In this contribution we present experimental analysis supported with quantum chemical DFT calculations which allowed us to propose a simple, physically transparent model to predict the impact of alloying on the local electronic structure of different sites in alloys and on the local chemical reactivity. The model was developed through studies of a number of Pt alloys. The central feature of the model is that hybridization of d-orbitals in alloys does not lead to significant charge transfermore » between the constituent elements in the alloy, and therefore the width of the local density of d-states projected on a site, which is easily calculated from tabulated parameters, is an excellent descriptor of the chemical reactivity of the site.« less