THEORETICAL PREDICTION OF PREFERRED BONDING SITES - A CRITICAL ANALYSIS BASED ON A MODEL SYSTEM

被引:6
作者
MATOS, M
NETO, JBL
机构
[1] Departamento de Física, Pontifícia Universidade Católica do Rio de Janeiro, 22452 Rio de Janeiro, RJ
关键词
D O I
10.1016/0039-6028(91)90936-M
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We develop a critical analysis of different procedures found in the literature to theoretically predict preferred bonding sites in chemisorption. Geometrical and edge effects, which appear in the calculation of adatom-surface potential energy, parallel to the surface, are investigated within the embedding LSA and finite-cluster methods. A systematic study of convergence for different adsorbate sites is performed on the chemisorption of H on a model tungsten (100) surface. By using arguments based strictly on the convergence analysis and on the N-variational character of the LSA method, we show that, due to embedding, the latter formalism eliminates geometrical (shape) effects of the finite-N representation; it is shown to be suitable to represent in general the potential energy curve as a function of parallel coordinates. It is also shown that finite-cluster models may lead to erroneous interpretation. On the other hand, certain kinds of cluster geometries present a smooth convergence for the binding energy, contrary to other geometries investigated in previous works. This fact leaded to a suggestion for the best procedure to compare cluster binding energies of different sites in the cubium model.
引用
收藏
页码:439 / 450
页数:12
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