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Transition metal atoms on oxide supports density functional calculations
Author(s) -
Halim W. S. Abdel,
Shalabi A. S.,
Soliman K. A.
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21806
Subject(s) - chemistry , adsorption , unpaired electron , density functional theory , oxide , covalent bond , metal , transition metal , crystallography , vacancy defect , valence (chemistry) , valence electron , ground state , band gap , electron , computational chemistry , atomic physics , materials science , molecule , catalysis , physics , biochemistry , optoelectronics , organic chemistry , quantum mechanics
The adsorption properties of Cu, Ag, Ni, and Pd atoms on O 2− , F, and F + sites of MgO, CaO, SrO, and BaO (001) surfaces have been studied by means of density functional calculations. The examined clusters were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces. The adsorption properties have been analyzed with reference to the basicity and energy gap of the oxide support in addition to orbital interactions. While the free Ni d 9 s 1 triplet ground state is preserved on adsorption on the O 2− sites of MgO, CaO, and SrO surfaces, it is no longer preserved on the O 2− site of BaO. For all adsorbates considered, adsorption is found to be stronger on F + sites compared with regular O 2− sites. While on the O 2− site, Pd and Ni form the most stable complexes, on the F site, Pd and Cu form the most stable counterparts. On the F + site, the single valence electron of Cu and Ag atoms couples with the unpaired electron of the vacancy forming a covalent bond. As a result, the adsorption energies of these atoms on the F + site are stronger than those on the F and O 2− sites. The adsorption properties correlate linearly with the basicity and energy gap of the oxide support in addition to orbital interactions. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009