INVESTIGADORES
PATRITO Eduardo Martin
artículos
Título:
On the nature of the SO42-/Ag(111) and SO42-/Au(111) surface bonding
Autor/es:
E. M. PATRITO; P. PAREDES OLIVERA; HARRELL SELLERS
Revista:
SURFACE SCIENCE
Editorial:
ELSEVIER SCIENCE BV
Referencias:
Lugar: Amsterdam; Año: 1997 vol. 380 p. 264 - 282
ISSN:
0039-6028
Resumen:
The nature of sulfate-Ag(lll) and sulfate-Au(lll) surface bonding has been investigated at the SCF+MP2 level of theory. Convergence of binding energy with cluster size is investigated and, unlike neutral adsorbates, large clusters are required in order to obtain reliable binding energies. In the most stable adsorption mode, sulfate binds to the surface via three oxygen atoms tC3vsymmetry) with a binding energy of 159.3 kcal/mol on Ag(111) and 143.9 kcal/mol on Au(lll). The geometry of adsorbed sulfate was optimized at the SCF level. While the bond length between sulfur and the oxygens coordinated to the surface increases, the sulfur uncoordinated oxygen bond length decreases. This weakening and strengthening of the bonds, respectively, is consistent withbond order conservation in adsorbates on metal surfaces. Although a charge transfer of 0.4 electrons towards the metal is observed, the adsorbate remains very much sulfate-like. The molecular orbital analysis indicates that there is also some charge back-donation towards unoccupied orbitals of sulfate. This results in an increased electron density around sulfur as revealed in the electron density difference maps. Analysis of the Laplacian of the charge density of free sulfate provides a suitable framework to understand the nature of the different charge transfer processes and allows us to establish some similarities with the CO-- and SO2-metal bondings.