Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principles

Author(s)

Amador, Davi H. T. ; Sambrano, Julio R. ; Gargano, Ricardo ; de Macedo, Luiz Guilherme M.

• Document type: Journal article
• Source: Journal of Molecular Modeling; v. 23, n. 3 MAR 2017.
• Web of Science Citations: 4

Abstract

The aqueous solvation of Th and Np in the IV oxidation state was examined using cluster models generated by Monte Carlo simulations and density functional theory embedded within the COSMO continuum model to approximate the effect of bulk water. Our results suggest that the coordination number (CN) for both Th(IV) and NP(IV) should be 9, in accordance to some experimental and theoretical results from the literature. The structural values for average oxygen-metal distances are within 0.01 angstrom compared to experimental data, and also within the experimental error. The calculated Delta G(Sol)(0) are in very good agreement with experimental reported values, with deviations at CN = 9 lower than 1% for both Th(IV) and Np(IV). The hydrolysis constants are also in very good agreement with experimental values. Finally, our methodology has the advantage of using a GGA functional (BP86) that not only makes the calculations more affordable computationally than hybrid functional or ab initio molecular dynamics simulations (Car-Parrinello) calculations, but also opens the perspective to use resolution of identity (RI) calculations for more extended systems. (AU)

• FAPESP's process: 13/07296-2 - CDMF - Center for the Development of Functional Materials
• Grantee: Elson Longo da Silva
• Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC
• FAPESP's process: 16/07954-8 - Computational study of zinc oxide pure and doped with transition metals: bulk, surfaces, interfaces and nanotubes
• Grantee: Naiara Letícia Marana
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate
• FAPESP's process: 16/07476-9 - Porous nanotubes of carbon and inorganic semiconductors: a computational study
• Grantee: Julio Ricardo Sambrano
• Support Opportunities: Regular Research Grants
• FAPESP's process: 13/19713-7 - Computational study of zinc oxide pure and doped with transition metals: bulk, surfaces, interfaces and nanotubes
• Grantee: Naiara Letícia Marana
• Support Opportunities: Scholarships in Brazil - Doctorate