화학공학소재연구정보센터
Inorganic Chemistry, Vol.42, No.21, 6701-6708, 2003
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 Ge-g(z) clusters (z = -6, -4, -3, -2, 0, +2, and +4) starting from three different initial configurations. Double-zeta 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-9(2-) is the tricapped trigonal prism expected by Wade's rules for a 2n + 2 skeletal electron structure. An elongated tricapped trigonal prism is the global minimum for Ge-9(4-) similar to the experimentally found structure for the isoelectronic Bi-9(5+). However, the capped square antiprism predicted by Wade's 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 Ge-9(6-), with the latter being lower in energy by 3.66 kcal/mol and far less distorted. The global minimum for the hypoelectronic Ge-9 is a bicapped pentagonal bipyramid. However, a second structure for Ge-9 only 4.54 kcal/mol above this global minimum is the C-2v flattened tricapped trigonal prism structure found experimentally for the isoelectronic Tl-9(9-). For the even more hypoelectronic Ge-9(2+), the lowest energy structure consists of an octahedron fused to two trigonal bipyramids. For Ge-9(4+), the global minimum is an oblate (squashed) pentagonal bipyramid with two pendant Ge vertices.