Structural and electronic properties of Bin (n = 2-14) clusters from density-functional calculations

Abstract

The structural and electronic properties of Bi n (n = 2-14) clusters have been systematically studied using gradient-corrected density-functional theory. For each cluster size, a number of structural isomers were constructed and optimized to search for the lowest-energy structure. The competition of several structural patterns such as cages, superclusters, and layered structures leads to the alternating appearance of these configurations as global minima. Although the tendency of Bi to form puckered-layer structures is already well-known, the electronic states of Bi n clusters are still far from that of the bulk. As well, a remarkable even-odd atom number oscillation is observed in the structural and electronic properties of the clusters, implying that the stability of Bi n clusters is mainly dominated by the electron shell effect rather than by geometrical packing. The theoretically calculated values for electron affinities agree well with available experimental data.