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Electronic Spectroscopy and Nanocalorimetry of Hydrated Magnesium Ions [Mg(H2O)n]+, n = 20–70: Spontaneous Formation of a Hydrated Electron?

Abstract

Hydrated singly charged magnesium ions [Mg(H2O)n]+ are thought to consist of an Mg2+ ion and a hydrated electron for n > 15. This idea is based on mass spectra, which exhibit a transition from [MgOH(H2O)n-1]+ to [Mg(H2O)n]+ around n = 15–22, black-body infrared radiative dissociation, and quantum chemical calculations. Here, we present photodissociation spectra of size–selected [Mg(H2O)n]+ in the range of n = 20–70 measured for photon energies of 1.0–5.0 eV. The spectra exhibit a broad absorption from 1.4 to 3.2 eV, with two local maxima around 1.7–1.8 eV and 2.1–2.5 eV, depending on cluster size. The spectra shift slowly from n = 20 to n = 50, but no significant change is observed for n = 50–70. Quantum chemical modeling of the spectra yields several candidates for the observed absorptions, including five- and six-fold coordinated Mg2+ with a hydrated electron in its immediate vicinity, as well as a solvent-separated Mg2+/e- pair. The photochemical behavior resembles the one of the hydrated electron, with barrierless interconversion into the ground state following the excitation.

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Publication details

The article was accepted on 07 Dec 2018 and first published on 10 Dec 2018


Article type: Paper
DOI: 10.1039/C8FD00204E
Citation: Faraday Discuss., 2018, Accepted Manuscript
  • Open access: Creative Commons BY license
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    Electronic Spectroscopy and Nanocalorimetry of Hydrated Magnesium Ions [Mg(H2O)n]+, n = 20–70: Spontaneous Formation of a Hydrated Electron?

    T. Taxer, M. Oncak, E. Barwa, C. van der Linde and M. K. Beyer, Faraday Discuss., 2018, Accepted Manuscript , DOI: 10.1039/C8FD00204E

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