Very little is known about the crystal chemistry of neptunyl peroxide compounds compared to their uranium analogs. We recently studied a neptunyl peroxide monomer Ca2[NpO2(O2)3].9H2O, which is the first Np (VI)-based peroxide compound that has been characterized and it is isostructural with its uranium counterpart. The crystal structure has the reported longest Np(VI)-Oyl bond length of 1.842(7) Å. Computationally we probed the oxidation state, bond lengths of the monomer unit and differences in Raman spectra of uranyl and neptunyl triperoxide compounds. We further investigated the Np24 nanoscale cage cluster that is topologically identical to U24. Unlike its uranium analogue, the Np24 compound contains a mixture of metal valances and there are four different types of Np centers in the crystal structure. We used density functional theory along with experimental support to assign the oxidation state of various crystallographically different Np centers. Our study reveals that charge transfer may occur from Np (V) to Np (VI), which may explain the dark color of the Np24 compound.

Computational study of neptunium compounds: From monomer to mixed valence Np24 clusters

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.