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Abstract:
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The electronic structure and the spectroscopic properties of
[Pt(NH3)4][Au(CN)2]2, [Pt(NH3)4][Ag(CN)2]2, [Pt(CNCH3)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 timedependent
(TD) method at the HF, B3LYP, and PBE levels. The [Pt(NH3)4][M(CN)2]2
(M Au, Ag) complexes showed a 1(d * 3 p ) 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(d * 3 *) transition associated with a metal-to-metal and
ligand charge transfer. The values obtained theoretically are in agreement with the
experimental range. |