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Oxidizing Metal Oxides with Polynuclear Superhalogen: An ab Initio Study

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journal contribution
posted on 24.08.2018, 00:00 by Celina Sikorska
The ability of metal oxides (CoO, CuO, MgO, MnO2, NiO, SiO2, TiO2, and ZnO) to form stable systems with polynuclear superhalogen (i.e., Mg3F7) is examined on the basis of theoretical considerations supported by ab initio calculations. It is demonstrated that the MeOn (n = 1, 2) molecules (such as CoO, CuO, MgO, MnO2, NiO, TiO2, ZnO) should form stable and strongly bound (MeOn)+(superhalogen) salts when combined with the Mg3F7 superhalogen radical (acting as an oxidizing agent). This conclusion is supported by providing: (i) structural deformation of superhalogen upon ionization, (ii) predicted charge flow between each MeOn and superhalogen (which allows estimating the amount of electron density withdrawn from MeOn molecule during the ionization process), (iii) the localization of the spin density distribution, and (iv) the interaction energies and vertical ionization potentials (VIPs) for the compounds obtained at the CCSD­(T)/6-311+G­(d) level of theory. On the other hand, the Mg3F7 superhalogen was found to be incapable of ionizing molecules whose adiabatic ionization potentials (AIPs) exceed 12 eV (e.g., SiO2). I believe that the results provided in this contribution may likely be of prospective relevance in the future studies on the issue of binding and preventing metal oxide nanoparticles aggregation in the environment before they occur harmful to human health and environment.

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