Adsorption of d-metal atoms on the regular MgO(001) surface: Density functional study of cluster models embedded in an elastic polarizable environment
Source abstract
Abstract
Structure and bonding of complexes formed by 17 different single transition metal atoms (Cu, Ag, Au; Ni, Pd, Pt; Co, Rh, Ir; Fe, Ru, Os; Mn, Re; Cr, Mo, W) with oxygen sites of the regular MgO(001) surface were studied computationally. We employed an all-electron scalar-relativistic density functional method in combination with our novel scheme of cluster models embedded in an elastic polarizable environment that allows one to account for substrate relaxation. Even on a rigid substrate such as ideal MgO(001), adsorbate-induced relaxation noticeably affects structure and stability of surface complexes. For more reliable estimates, we calculated adsorption energies with two different gradient-corrected exchange-correlation functionals, BP86 and PBEN. More than one electron configuration was considered for metal atoms exhibiting high-spin states adsorption complexes. Within one group of the periodic table, 3d-atoms, in general, were found to adsorb more strongly than 4d-atoms, but weaker than 5d-atoms. In line with our previous studies of selected d-metal atoms adsorbed on oxides, the surface complexes considered did now show any indication of metal oxidation.
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Research context
OpenAlex topics: Catalytic Processes in Materials Science · Advanced Chemical Physics Studies · Copper-based nanomaterials and applications
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References (40)
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40. As mentioned in Sect. 3, the adsorption energy for the complex Co/MgO was calculated with respect to the atomic energy of the DF ground state configuration d8s1 computed to be 0.63 eV more stable than the experimental ground state configuration d7s2. Using the latter experimental atomic configuration as reference would result in a binding energy of 1.85 eV for a Co adatom; this value is in the range of the binding energies for the “neighboring” Ni/MgO and Fe/MgO systems. See also the discussion elsewhere on the reliability of DF atomic references [18, 19]