Geometric structure of the magic number clusters Li_nNa_8-n, Na_nK_8-n, and K_nLi_8-n

Article type: Research Article

Authors: Fournier, R.

Affiliations: York University, 4700 Keele Street, Toronto, ON, Canada, M3J 1P3. E-mail: [email protected]

Abstract: The mixed alkali clusters LinNa8-n, LinK8-n, and NanK8-n were studied by Kohn-Sham theory with a gradient corrected (PBE) exchange-correlation functional. Geometry optimization was done with a Tabu Search algorithm to find possible global minima, followed by local optimization with a quasi-Newton method. For the pure clusters and all NanKm mixed clusters, the predicted global minimum is a dodecahedron having D2d symmetry in its ideal form. There are various structures among the predicted global minima of LinNam and LinKm: they all have in common that the Lin subunit achieves maximal coordination and forms a compact core at, or near, the center of the cluster. The clusters LinNam and LinKm all have near zero asphericity, in line with the prediction of the ellipsoidal jellium model for 8 electrons, and the asphericity in nonzero but small in all other clusters. The clusters Li4Na4, Na4K4, and K4Na4 each have the four atoms of the lighter element near the center of mass and these clusters are more stable than those of other compositions. Calculated ionization potentials and static dipole polarizabilities agree rather well with experimental values but do not allow a structure assignment to be made.

Keywords: Clusters, structure, global optimization, density functional theory

DOI: 10.3233/JCM-2008-84-609

Journal: Journal of Computational Methods in Sciences and Engineering, vol. 8, no. 4-6, pp. 331-342, 2008