On the electronic structure of [W(WS 4) 2] 2−

Abstract

The ground-state electronic structure of W 3S 8 2− has been calculated using the relativistic SCF-MS-X α method. The results confirm a formal oxidation state of +2 for the central tungsten atom and a + 6 oxidation state for the terminal ones. A W|W σ bond is detected within the 7 a 1 g molecular orbital leading to a W|W bond order of 1/2. The energy order of the X α MOs of ligand field interest, localized on the central metal ion, is explained based on the simple angular overlap approach taking into consideration the W|W interactions.