Electronic properties of metal clusters (Ni13 to Ni87) and implications for chemisorption

First principles calculations of the electronic properties of Ni clusters (up to Ni₈₇) are reported. It is found that the ionization potential (IP) converges to bulk values (work function) by Ni₄₃, whereas the electron affinity (EA) is off by 2.5 eV, even for Ni₈₇. The conduction band of ～16 eV appears converged by Ni₈₇. It is found that the electron density for surface atoms is significantly lower than the bulk value. The significance of these results for chemisorption on small metallic clusters and for modelling of chemisorption on bulk surfaces is discussed.