Density Functional Theory Study of Nine-Atom Germanium Clusters: Effect of Electron Count on Cluster Geometry

Density functional theory (DFT) at the hybrid B3LYP level has been applied to the germanium clusters Ge9z clusters (z = -6, -4, -3, -2, 0, +2, and +4) starting from three different initial configurations. Double-(chi) quality LANL2DZ basis functions extended by adding one set of polarization (d) and one set of diffuse (p) functions were used. The global minimum for Ge^2- 9 is the tricapped trigonal prism expected by Wadeʹs rules for a 2n + 2 skeletal electron structure. An elongated tricapped trigonal prism is the global minimum for Ge^4- 9 similar to the experimentally found structure for the isoelectronic Bi95+. However, the capped square antiprism predicted by Wadeʹs rules for a 2n + 4 skeletal electron structure is only 0.21 kcal/mol above this global minimum indicating that these two nine-vertex polyhedra have very similar energies in this system. Tricapped trigonal prismatic structures are found for both singlet and triplet Ge96-, with the latter being lower in energy by 3.66 kcal/mol and far less distorted. The global minimum for the hypoelectronic Ge9 is a bicapped pentagonal bipyramid. However, a second structure for Ge9 only 4.54 kcal/mol above this global minimum is the C2v flattened tricapped trigonal prism structure found experimentally for the isoelectronic Tl99-. For the even more hypoelectronic Ge92+, the lowest energy structure consists of an octahedron fused to two trigonal bipyramids. For Ge94+, the global minimum is an oblate (squashed) pentagonal bipyramid with two pendant Ge vertices.