Evolution of the Electronic Structure of Small Vanadium Clusters from Molecular to Bulklike

The evolution of the electronic structure of $V_n$ clusters is probed by photoelectron spectroscopy (PES) at 3.49, 4.66, and 6.42 eV photon energies. Three regions of spectral evolution are distinctly observed as a function of cluster size: molecularlike behavior for $n=3\mathrm{}–12$; transition from molecular to bulklike for $n=13\mathrm{}–17$; gradual convergence to bulk for $n>\mathrm{}17\mathrm{}$, for which a surfacelike feature is observed to slowly merge into the bulk feature near $n=60\mathrm{}$. The PES spectra provide an atom-by-atom view of the evolution of the electronic structure of the ${\mathrm{V}}_n$ clusters from molecular to bulklike.