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Photoelectron Imaging Study of the Diplatinum Iodide Dianions [Pt2I6]2– and [Pt2I8]2–

Gibbard, Jemma A. and Verlet, Jan R. R. (2022) 'Photoelectron Imaging Study of the Diplatinum Iodide Dianions [Pt2I6]2– and [Pt2I8]2–.', The Journal of Physical Chemistry A, 126 (22).


Photoelectron spectroscopy has been used to study the electronic structure, photodetachment, and photodissociation of the stable diplatinum iodide dianions [Pt2I6]2– and [Pt2I8]2–. Photoelectron spectra over a range of photon energies show the characteristic absence of low kinetic energy photoelectrons expected for dianions as a result of the repulsive Coulomb barrier (RCB). Vertical detachment energies of ∼1.6 and ∼1.9 eV and minimum RCBs of ∼1.2 and ∼1.3 eV are reported for [Pt2I6]2– and [Pt2I8]2–, respectively. Both of the diplatinum halides exhibit three direct detachment channels with distinct anisotropies, analogous to the previously reported spectra for PtI2– and PtI–, suggesting a platinum-centered molecular core that dominates the photodetachment. Additionally, evidence for two-photon photodissociation and subsequent photodetachment channels producing I– are observed for both dianions. Finally, an unexplained feature is observed at photon energies around 3 eV, whose origin is considered. Our work highlights the complex electronic structure of the heavy platinum-halide dianions that are characterized by a dense manifold of electronic states.

Item Type:Article
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Publisher statement:This is an open access article under the CC BY license (
Date accepted:No date available
Date deposited:18 July 2022
Date of first online publication:27 May 2022
Date first made open access:18 July 2022

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