New model of the electronic structure of the [Mo6X8(CN)6]6− clusters (XS, Se) based on the study of electron density distribution in the inner part of the Mo6 polyhedron

Abstract

AbstractThe geometric structure and bonding in [Mo6S8(CN)6]6− cluster were studied on the basis of quantum chemical ab initio and DFT (B3LYP) calculations with different basis sets. The geometry parameters of the Mo6S8 core are in good agreement with the available crystal structure data. The electron density in the inner part of the Mo6 octahedron is almost constant (∼0.04–0.06 e/au3). There is also noticeable electron density on the edges and faces of the Mo6S8 polyhedron. The model of the electronic structure of the cluster under consideration starts from the mobile electrons moving in the potential well of the spherical symmetry. The resulting states are classified according to orbital quantum number l (e.g., 1s, 1p, 1d, 1f). Subsequent crystal field splitting leads to observable consequence of the one electron states of the Oh point group symmetry. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004