PNNL

Abstract

Stability constants of simple reactions involving addition of the \ce{NO3$^-$} ion to hydrated metal complexes, [M(H$_2$O)$_x$]$^{n+}$ are calculated with a computational workflow developed using cloud computing resources. The computational workflow performs conformational searches for metal complexes at both low and high levels of theories in conjunction with a continuum solvation model (CSM). The low-level theory is mainly used for the initial conformational searches, which are complemented with high-level density functional theory conformational searches in the CSM framework to determine the coordination chemistry relevant for stability constant calculations. In this regard, the lowest energy conformations are found to obtain the reaction free energies for the addition of one \ce{NO3}$^{-}$ to [M(H$_2$O)$_x$]$^{n+}$ complexes, where M represents Fe(II), Fe(III), Sr(II), Ce(III), Ce(IV), and U(VI), respectively. Structural analysis of hundreds of optimized geometries at high-level theory reveals that \ce{NO3}$^{-}$ coordinates with Fe(II) and Fe(III) in either a monodentate or bidentate manner. Interestingly, the lowest-energy conformations of Fe(II) metal-nitrate complexes exhibit monodentate or bidentate coordination with a coordination number of 6 while the bidentate seven-coordinated Fe(II) metal-nitrate complexes are approximately 2 kcal/mol higher in energy. Notably, for Fe(III) metal-nitrate complexes, the bidentate seven-coordinated configuration is more stable than the six-coordinated Fe(II) complexes (monodentate or bidentate) by a few thermal energy units. In contrast, Sr(II), Ce(III), Ce(IV), and U(VI) metal ions predominantly coordinate with \ce{NO3}$^{-}$ in a bidentate manner, exhibiting typical coordination numbers of 7, 9, 9, and 5, respectively. Stability constants are accordingly calculated using linear free energy approaches to account for the systematic errors and good agreements are obtained between the calculated stability constants and the available experimental data.