Density functional theory was employed to study the stabilities and chemical activities of transition metal carbides. Here we take the well-known Mo carbides and Ti carbides as an example. Different kinds of structures including the bulk surfaces [Mo(2)C(001), MoC(001), and TiC(001)] and metcars [Mo(8)C(12) and Ti(8)C(12)] are taken into consideration. Systematic studies show that by raising the C coordination number of the metal atoms in the carbides, in general the stability of the carbides increases (metcars are an exception since they include both high-coordinated and low-coordinated metal atoms.); at the same time, the chemical activities of the carbides decrease due to a downshift of the metal d-band center (ligand effect). Considering the better catalysts those that combine high stability and moderate chemical activity, our results suggest that the catalytic potential of Mo carbide systems should decrease in the following sequence: Mo(8)C(12)>Mo(2)C(001) or MoC(001)>pure Mo(110). In spite of having the largest C/Mo ratio, the metcar appears as the most attractive system. Our studies also indicate that the "magic" behavior of metcars is not unique for Mo carbides. Similar behavior is also observed for Ti carbides. This implies that nanoparticles like metcar species could exhibit better performances than the corresponding bulk metal carbides as catalysts.
(c) 2004 American Institute of Physics.