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Coordination‐Resolved Spectrometrics of Local Bonding and Electronic Dynamics of Au Atomic Clusters, Solid Skins, and Oxidized Foils
Author(s) -
Yu Wang,
Bo Maolin,
Huang Yongli,
Wang Yan,
Li Can,
Sun Chang Q.
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500171
Subject(s) - binding energy , x ray photoelectron spectroscopy , bond length , chemistry , bond energy , chemical physics , bond order , chemical bond , valence bond theory , electron , atomic physics , materials science , crystallography , molecule , molecular orbital , physics , nuclear magnetic resonance , organic chemistry , crystal structure , quantum mechanics
By using combination of bond‐order–length–strength (BOLS) correlation, the tight‐binding (TB) approach, and zone‐selective photoelectron spectroscopy (ZPS), we were able to resolve local bond relaxation and the associated 4f 7/2 core‐level shift of Au atomic clusters, Au(100, 110, 111) skins, and Au foils exposed to ozone for different lengths of time. In addition to quantitative information, such as local bond length, bond energy, binding‐energy density, and atomic cohesive energy, the results confirm our predictions that bond‐order deficiency shortens and stiffens the bond between undercoordinated atoms, which results in local densification and quantum entrapment of bonding electrons. The entrapment perturbs the Hamiltonian, and hence, shifts the core‐level energy accordingly. ZPS also confirms that oxidation enhances the effect of atomic undercoordination on the positive 4f 7/2 energy shift, with the associated valence electron polarization contributing to the catalytic ability of undercoordinated Au atoms.