Electronic structure and UV spectrum of hexachloroplatinate dianions in vacuo
Sydney H Kaufman1, J Mathias Weber, Markus Pernpointner
1JILA and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
Abstract:
We present a joint experimental and theoretical study of the electronic spectrum of hexachloroplatinate dianion. We have measured electronic photodissociation and photodetachment spectra of mass-selected PtCl6(2-) ions in vacuo and compare these with calculated band positions from time-dependent density functional theory and from relativistic calculations. Excitation of an electronic transition of the dianion leads to resonant enhancement of the photodetachment cross section superimposed on direct detachment. Photoexcitation results in loss of Cl(-) and Cl(0), depending on photon energy. The photofragmentation spectrum for formation of the PtCl4(-) fragment ion mirrors the UV∕vis absorption spectrum of PtCl6(2-) in solution with a small solvatochromic shift.
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