Electronic Structure of Transition Metal Clusters from Density Functional Theory. 1. Transition Metal Dimers

Abstract

The electronic structure of transition metal clusters is of great interest for a wide range of investigations including the properties of catalytic systems. In order to determine the electronic structure of transition metal dimers, calculations of total energies and geometry optimizations have been carried out on Pd2, Rh2, Ru2, Au2, and Pt2 dimers as well as PdPt, RhPt, RuPt, and PdAu dimers using a method based on density functional theory (DFT) with nonlocal (NLDFT) correction. The typical applications of DFT for the determination of the general features of electronic structure of Pd4, Rh4, Au4, and Pt4 clusters have also been performed at the level of NLDFT using the norm-conserving pseudopotential method (NCPP). The results of these calculations are in good qualitative agreement with those of the previous DFT calculations. The Mulliken charge analysis has indicated that a charge transfer occurs between the atoms of Pd and Pt, as well as between Rh and Pt atoms, Ru and Pt atoms, and Pd and Au atoms in the corresponding bimetallic dimers. Finally, this DFT method is expected to be very helpful to predict the electronic structure of small metal cluster systems.