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

Gibbard, Jemma A.; Verlet, Jan R.R.

Abstract

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.

Citation

Gibbard, J. A., & Verlet, J. R. (2022). Photoelectron Imaging Study of the Diplatinum Iodide Dianions [Pt2I6]2– and [Pt2I8]2–. The Journal of Physical Chemistry A, 126(22), https://doi.org/10.1021/acs.jpca.2c02008

• Journal Article Type: Article
• Online Publication Date: May 27, 2022
• Publication Date: 2022
• Deposit Date: Jul 18, 2022
• Publicly Available Date: Jul 18, 2022
• Journal: The Journal of Physical Chemistry A
• Print ISSN: 1089-5639
• Electronic ISSN: 1520-5215
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 126
• Issue: 22
• DOI: https://doi.org/10.1021/acs.jpca.2c02008
• Public URL: https://durham-repository.worktribe.com/output/1197373