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Adsorption of d-metal atoms on the regular MgO(001) surface: Density functional study of cluster models embedded in an elastic polarizable environment

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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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Authors and Affiliations

  1. Institut für Physikalische und Theoretische Chemie, Technische Universität München, 85747, Garching, Germany

    K.M. Neyman, C. Inntam, R. Kosarev & N. Rösch

  2. Institute of Chemistry and Chemical Technology, Russian Academy of Sciences, 660049, Krasnoyarsk, Russia

    V.A. Nasluzov

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  1. K.M. Neyman
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  2. C. Inntam
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  3. V.A. Nasluzov
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  4. R. Kosarev
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  5. N. Rösch
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Correspondence to K.M. Neyman.

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PACS

68.43.Bc; 68.43.Fg; 71.15.Nc; 82.65.+r; 68.35.Ct; 68.43.-h; 73.20.Hb; 71.15.Mb; 75.70.Cn

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Neyman, K., Inntam, C., Nasluzov, V. et al. Adsorption of d-metal atoms on the regular MgO(001) surface: Density functional study of cluster models embedded in an elastic polarizable environment. Appl. Phys. A 78, 823–828 (2004). https://doi.org/10.1007/s00339-003-2437-5

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  • DOI: https://doi.org/10.1007/s00339-003-2437-5

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