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 +1 Li n −1 X and n Li n −1 X + ( 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 Li n −1 X clusters can be derived from capping an X atom over the high-spin Li n −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 Li n −1 X (X = Li, Na and K, n = 2–8) neutral and cationic species, 5 Li 3 X and 3 Li 2 X + are predicted to be of high stability, which can be explained by valence bond theory.