Electronic structure of small titanium clusters: Emergence and evolution of the 3d band.

Abstract

The electronic structure of titanium clusters $({\mathrm{Ti}}_{n},n\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}3--65)$ is probed by size-selected anion photoelectron spectroscopy. It is observed that the 3d band emerges at the eight-atom cluster beyond which the d band broadens and evolves toward that of the bulk. The electronic structure of the titanium clusters is found to become bulklike at relatively small cluster sizes. This is discussed in terms of the delocalization of the titanium 3d orbitals and the implications for the cluster structures.