Abstract

The electronic structure and the spectroscopic properties of [Pt(NH 3)4][Au(CN)2]2, [Pt(NH 3)4][Ag(CN)2]2, [Pt(CNCH 3)4][Pt(CN)4], and [Pt(CNCH3) 4][Pd(CN)4] were studied at the HF, MP2, B3LYP, and PBE levels. In all the complexes, it was found that the nature of the intermetal interactions is consistent with the presence of a high-ionic contribution (90%) and a dispersion-type interaction (10%). The absorption spectra of these complexes were calculated by the single-excitation time-dependent (TD) method at the HF, B3LYP, and PBE levels. The [Pt(NH3)4][M(CN) 2]2 (M = Au, Ag) complexes showed a 1(dσ* → pσ) transition associated with a metal-metal charge transfer. On the other hand, the [Pt(CNCH3) 4][M(CN)4] (M = Pt, Pd) complexes showed a 1(dσ* → π*) transition associated with a metal-to-metal and ligand charge transfer. The values obtained theoretically are in agreement with the experimental range. © 2008 Wiley Periodicals, Inc.