Reliability of one‐electron approaches in chemisorption cluster model studies: Role of core‐polarization and core–valence correlation effects

摘要: Interaction of atomic oxygen with a Cu5 (Ag5) cluster model simulating the fourfold chemisorption on Cu(100) and Ag(100) has been studied at self‐consistent‐field (SCF) configuration interaction (CI) levels using one‐electron pseudopotentials to describe inner shells metal atoms. Core‐polarization effects are introduced by means second‐order perturbation method. Results show method be reliable that there is no need for any molecular adjustment pseudopotential. Nondynamical dynamical valence correlation found very important. The separability analyzed comparison previous calculations explicitly including d electrons Core–valence decrease energy calculated CI level shown important not only from quantitative point view but also qualitative one because different electronic...