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...
| Main Authors: | , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
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2013
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| Online Access: | https://hdl.handle.net/10356/98562 http://hdl.handle.net/10220/17161 |
| _version_ | 1824455710242504704 |
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| author | Sun, Changqing Qin, Wei Wang, Yan Huang, Yongli Zhou, Zhaofeng Yang, Chao |
| 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 |
| author_sort | Sun, Changqing |
| collection | NTU |
| 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. |
| first_indexed | 2025-02-19T03:42:32Z |
| format | Journal Article |
| id | ntu-10356/98562 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2025-02-19T03:42:32Z |
| publishDate | 2013 |
| record_format | dspace |
| spelling | ntu-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 |
| 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 |
| title | 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_short | 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 |
| topic | DRNTU::Science::Chemistry::Physical chemistry |
| url | https://hdl.handle.net/10356/98562 http://hdl.handle.net/10220/17161 |
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