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Title: Electronic structure and UV spectrum of hexachloroplatinate dianions in vacuo

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 PtCl{sub 6}{sup 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{sup −} and Cl{sup 0}, depending on photon energy. The photofragmentation spectrum for formation of the PtCl{sub 4}{sup −} fragment ion mirrors the UV/vis absorption spectrum of PtCl{sub 6}{sup 2−} in solution with a small solvatochromic shift.
Authors:
;  [1] ;  [2]
  1. JILA and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309 (United States)
  2. Physikalisch-Chemisches Institut, Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg (Germany)
Publication Date:
OSTI Identifier:
22251384
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 19; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; CROSS SECTIONS; DENSITY FUNCTIONAL METHOD; DISSOCIATION; ELECTRONIC STRUCTURE; IONS; PHOTOLYSIS; PLATINUM CHLORIDES; ULTRAVIOLET SPECTRA