Structure and stability of high-spin Lin−1X (n = 2-8, X = Li, Na, and K) clusters

The structures, relative stability and charge distributions in the maximum-spin n+1Lin−1X and nLin−1X+ (n =2-7, X = Li, Na and K) clusters have been studied with density functional calculations. We predicted the existence of a number of previously unknown cationic isomers. Our results revealed that all high-spin Lin−1X clusters can be derived from capping an X atom over the high-spin Lin−1. Larger heter-atoms favor to occupy outer positions in order to decrease geometrical reconstruction. The high-spin bimetallic clusters tend to holding three-dimensional geometry rather than planar form in low-spin situations whereas smaller ions adopt linear-like form to reduce their repulsive force among atoms. In various high-spin Lin−1X (X = Li, Na and K, n = 2-8) neutral and cationic species, 5Li3X and 3Li2X+ are predicted to be of high stability, which can be explained by valence bond theory.