Geometrical and Electronic Structure of the Pt7 Cluster: A Density Functional Study Wei Quan Tian, Maofa Ge, B. R. Sahu, ll Dianxun Wang,
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Abstract: We present a study on the structural and electronic properties of the Pt7 cluster by using density functional theory within the generalized gradient approximation for the exchange and correlation. The structures, relative stabilities, and vibrational frequencies of various isomers are calculated and compared with the well-studied Au7 cluster. The ground state of the Pt7 cluster favors a three-dimensional geometry-two-dimensional local minima are not located-whereas for its neighbor, gold heptamer, a two-dimensional geometry is favored. The most stable isomer of Au7 is found to be an edge-capped rhombus structure and an edge-capped tetrahedron structure is found to be the most stable three-dimensional local minimum. The ground state of the Pt7 cluster is found to be a coupled tetragonal pyramid structure with the quintet state in contrast to a pentagonal bipyramid structure obtained by semiempirical molecular dynamics calculation. The natural orbital analysis shows that the overall charge transfer is from 6s to 5d orbitals in the Pt? cluster, whereas in An? cluster it is from 5d to 6s. The molecular orbital picture shows thai the bonding orbitals are due to the hybridization between 5d and 6s molecular orbitals in Pt7 cluster, and the nonbonding and antibonding orbitals lie close to the highest occupied molecular orbital. This may be compared with the Au7 electronic structure, where the nonbonding and antibonding orbitals mainly consists of 5d6s hybridized molecular orbitals, |