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Surfaces
Gianfranco Pacchioni*[a]
CHEMPHYSCHEM 2003, 4, 1041 1047 DOI: 10.1002/cphc.200300835 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1041
conductor, or another oxide).[9, 10] This implies also a detailed
mapping of the surface defects, a difficult task because of their
low concentration and of the great variety of possible defect
situations. To give just one example of the variety of defects
present at oxide surfaces, we mention here the case of MgO.
Magnesium oxide is a particularly well-studied oxide because the
structure of the (100) single crystal surface is extremely flat,
clean, and stoichiometric. A great effort has been made in recent
years to characterize the MgO surface better, in particular for thin
films or polycrystalline forms,[11] and about a dozen different
types of defects and irregularities have been identified and
described in the literature, Figure 3 and Table 1. The identifica-
tion and classification of these defects is a formidable task, but is
Figure 2. STM images of oxygen vacancies (bright spots) at the (110) surface of
of fundamental importance. In fact, the presence of appreciable
TiO2 (courtesy of R. Schaub and F. Besenbacher)
1042 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org CHEMPHYSCHEM 2003, 4, 1041 1047
Oxide Surfaces
anion vacancy Fmnc (m 0,1,2; n 3,4,5) missing oxygen with trapped electrons[3134]
cation vacancy Vm nc (m 0,1,2; n 3,4,5) missing cation with holes at O neighbors[35]
Mg and O divacancy VMgO cation and anion vacancy[36]
anion vacancy aggregate Mm (m 0,1) aggregate of two or more O vacancies[37]
low-coordinated cation Mg2nc (n 3,4) coordinatively unsaturated cation[38]
low-coordinated anion O2 nc (n 3,4) coordinatively unsaturated anion[39]
hydroxy group OH proton attached to O2 [40]
impurity atoms Mn/On ; Mg2/X2 substitutional cation (M Li, Ni, etc.) or anion (X S)[41]
oxygen radical O nc (n 3,4,5) hole trapped at O anion[42]
shallow electron traps MgOcorner(e ) trapped electrons at morphological sites (e.g., Mg23c)[43]
deep electron traps (M)(e ) pairs cation (H, Na, etc.) and electron pairs[44]
[a] nc is the coordination number of the center; 5c five-coordinated (100) terrace sites; 4c four-coordinated step or edge sites; 3c three-coordinated
corner sites.
CHEMPHYSCHEM 2003, 4, 1041 1047 www.chemphyschem.org 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1043
G. Pacchioni
1044 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org CHEMPHYSCHEM 2003, 4, 1041 1047
Oxide Surfaces
Figure 8. EPR spectra of an activated MgO surface exhibits the typical signal
assigned to trapped electrons (top); after exposure to N2 at 77 K the spectra
changes dramatically indicating the formation of a new species (center); the
simulated spectrum (bottom) indicates that the new species corresponds to the
N2 radical anion formed by electron transfer from the surface. Reproduced from
ref. [20], with permission of the American Chemical Society.
CHEMPHYSCHEM 2003, 4, 1041 1047 www.chemphyschem.org 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1045
G. Pacchioni
the most likely sites for the nucleation to occur, as demonstrated of the static and dynamic behavior of point defects at oxide
in Figure 10. It should be mentioned, however, that some surfaces.
theoretical studies cast doubts on this view, at least for the
transition-metal atoms at the right of the periodic table.[27] But
there is also another reason why these centers are important. For Acknowledgements
1046 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org CHEMPHYSCHEM 2003, 4, 1041 1047
Oxide Surfaces
[35] P. Baranek, G. Pinarello, C. Pisani, R. Dovesi, Phys. Chem. Chem. Phys. 2000, [42] G. Pinarello, C. Pisani, A. D'Ercole, M. Chiesa, M. C. Paganini, E. Giamello, O.
2, 3893. Diwald, Surf. Sci. 2001, 494, 95.
[36] L. Ojame, C. Pisani, J. Chem. Phys. 1998, 109, 10 984. [43] P. V. Sushko, J. L. Gavartin. A. L. Shluger, J. Phys. Chem. B 2002, 106, 2269.
[37] E. Miyoshi, Y. Miyake, S. Katsuki, Y. Sakai, J. Mol. Struct. (Theochem) 1988, [44] D. Ricci, C. Di Valentin, G. Pacchioni, P. V. Sushko, A. L. Shluger, E. Giamello,
451, 81. J. Am. Chem. Soc. 2003, 125, 738.
[38] J. Sauer, P. Ugliengo, E. Garrone, V. R. Saunders, Chem. Rev. 1994, 94, 2095.
[39] G. Pacchioni, J. M. Ricart, F. Illas, J. Am. Chem. Soc. 1994, 116, 10 152.
[40] O. Diwald, M. Sterrer, E. Knzinger, Phys. Chem. Chem. Phys. 2002, 4, 2811. Received: May 12, 2003 [M 835]
[41] L. Ackermann, J. D. Gale, C. R. A. Catlow, J. Phys. Chem. B 1997, 101, 10 028.
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