Bond order resolved 3d 5/2 and valence band chemical shifts of Ag surfaces and nanoclusters

Incorporating the tight-binding theory and the bond order–length–strength (BOLS) correlation into the X-ray photoelectron spectra of Ag(111) and (100) surfaces and the Auger electron spectra of Ag nanoparticles deposited on Al2O3 and CeO2 substrates has led to quantitative information of the 3d5/2 a...

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Main Authors: Sun, Changqing, Qin, Wei, Wang, Yan, Huang, Yongli, Zhou, Zhaofeng, Yang, Chao
Other Authors: School of Electrical and Electronic Engineering
Format: Article
Language:English
Published: 2013
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Online Access:https://hdl.handle.net/10356/98562
http://hdl.handle.net/10220/17161
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-985622020-03-07T13:56:08Z Bond order resolved 3d 5/2 and valence band chemical shifts of Ag surfaces and nanoclusters Sun, Changqing Qin, Wei Wang, Yan Huang, Yongli Zhou, Zhaofeng Yang, Chao School of Electrical and Electronic Engineering DRNTU::Science::Chemistry::Physical chemistry Incorporating the tight-binding theory and the bond order–length–strength (BOLS) correlation into the X-ray photoelectron spectra of Ag(111) and (100) surfaces and the Auger electron spectra of Ag nanoparticles deposited on Al2O3 and CeO2 substrates has led to quantitative information of the 3d5/2 and the valence binding energies of an isolated Ag atom and their shifts upon bulk, defect, surface, and nanocrystal formation. It is clarified that the globally positive energy shifts originate from the undercoordination-induced Goldschmidt–Pauling bond contraction and the associated local quantum entrapment and the heterocoordination-induced bond nature alteration at the particle–substrate interfaces. Perturbation to the Hamiltonian by atomic ill-coordination dictates the energy shift that is proportional to the bond energy at equilibrium. Theoretical reproduction of the measured spectroscopic data derived that the 3d5/2 energy of an isolated Ag atom shifts from 363.02 to 367.65 eV and the valence band center from 0.36 to 8.32 eV upon bulk formation. The extended Wagner plots revealed the coefficients of valence recharging and potential screening to be 1.21 and 1.56 for Ag interacting with Al2O3 substrate and 1.15 and 1.50 for Ag with CeO2, respectively. Exercises exemplify the enhanced capabilities of XPS and AES in determining quantitative information regarding the evolution of the local bond length, bond energy, binding energy density, and atomic cohesive energy, with the coordination and chemical environment. 2013-10-31T07:58:33Z 2019-12-06T19:56:53Z 2013-10-31T07:58:33Z 2019-12-06T19:56:53Z 2012 2012 Journal Article Qin, W., Wang, Y., Huang, Y., Zhou, Z., Yang, C., & Sun, C. (2012). Bond order resolved 3d 5/2 and valence band chemical shifts of Ag surfaces and nanoclusters. The journal of physical chemistry A, 116(30), 7892-7897. https://hdl.handle.net/10356/98562 http://hdl.handle.net/10220/17161 10.1021/jp304366z en The journal of physical chemistry A
institution Nanyang Technological University
building NTU Library
country Singapore
collection DR-NTU
language English
topic DRNTU::Science::Chemistry::Physical chemistry
spellingShingle DRNTU::Science::Chemistry::Physical chemistry
Sun, Changqing
Qin, Wei
Wang, Yan
Huang, Yongli
Zhou, Zhaofeng
Yang, Chao
Bond order resolved 3d 5/2 and valence band chemical shifts of Ag surfaces and nanoclusters
description Incorporating the tight-binding theory and the bond order–length–strength (BOLS) correlation into the X-ray photoelectron spectra of Ag(111) and (100) surfaces and the Auger electron spectra of Ag nanoparticles deposited on Al2O3 and CeO2 substrates has led to quantitative information of the 3d5/2 and the valence binding energies of an isolated Ag atom and their shifts upon bulk, defect, surface, and nanocrystal formation. It is clarified that the globally positive energy shifts originate from the undercoordination-induced Goldschmidt–Pauling bond contraction and the associated local quantum entrapment and the heterocoordination-induced bond nature alteration at the particle–substrate interfaces. Perturbation to the Hamiltonian by atomic ill-coordination dictates the energy shift that is proportional to the bond energy at equilibrium. Theoretical reproduction of the measured spectroscopic data derived that the 3d5/2 energy of an isolated Ag atom shifts from 363.02 to 367.65 eV and the valence band center from 0.36 to 8.32 eV upon bulk formation. The extended Wagner plots revealed the coefficients of valence recharging and potential screening to be 1.21 and 1.56 for Ag interacting with Al2O3 substrate and 1.15 and 1.50 for Ag with CeO2, respectively. Exercises exemplify the enhanced capabilities of XPS and AES in determining quantitative information regarding the evolution of the local bond length, bond energy, binding energy density, and atomic cohesive energy, with the coordination and chemical environment.
author2 School of Electrical and Electronic Engineering
author_facet School of Electrical and Electronic Engineering
Sun, Changqing
Qin, Wei
Wang, Yan
Huang, Yongli
Zhou, Zhaofeng
Yang, Chao
format Article
author Sun, Changqing
Qin, Wei
Wang, Yan
Huang, Yongli
Zhou, Zhaofeng
Yang, Chao
author_sort Sun, Changqing
title Bond order resolved 3d 5/2 and valence band chemical shifts of Ag surfaces and nanoclusters
title_short Bond order resolved 3d 5/2 and valence band chemical shifts of Ag surfaces and nanoclusters
title_full Bond order resolved 3d 5/2 and valence band chemical shifts of Ag surfaces and nanoclusters
title_fullStr Bond order resolved 3d 5/2 and valence band chemical shifts of Ag surfaces and nanoclusters
title_full_unstemmed Bond order resolved 3d 5/2 and valence band chemical shifts of Ag surfaces and nanoclusters
title_sort bond order resolved 3d 5/2 and valence band chemical shifts of ag surfaces and nanoclusters
publishDate 2013
url https://hdl.handle.net/10356/98562
http://hdl.handle.net/10220/17161
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