Thermodynamics of the Metal Carbonates and Bicarbonates of Mn, Co, Ni, Cu, and Zn Relevant to Mineral Energetics.

Abstract

The gas phase heats of formation of ground-state MCO3, M(HCO3)2, and M(HCO3)(OH), where M = Mn, Co, Ni, Cu, and Zn, have been predicted using the correlated molecular orbital theory at the CCSD(T) level extrapolated to the complete basis set limit using the Feller-Peterson-Dixon (FPD) approach. Cohesive energies of the carbonates were predicted based on the calculated gas phase and experimental solid heats of formation. Coulombic dissociation energies (CDEs) between metal cations and anions show a near-linear correlation with Shannon metal cation atomic radii, yet no correlation is found with the hardness of these cations. The total reaction dissociation energies (TRDEs) of transition metals are higher than their CDEs for the di-bicarbonates, in contrast to those for Mg and Ca based on our prior work. In addition to differences in the energies needed to prepare the transition metal dications, electron donation from the ligands to the 3d orbitals of open-shell transition metal dications from lone pairs of adjacent O atoms also plays a role. No electron donation from the ligands to the fully occupied 3d orbitals of Zn and Cd was found. Decomposition energies for generating MO, CO2, and/or H2O were calculated. Gas phase metal exchange energies only partially correlate with the electrochemical series for M(s) → M2+(aq). The FPD heats of formation were used to benchmark a range of density functional theory exchange-correlation functionals, including those commonly used in solid-state mineral calculations. None of the functionals provided chemical accuracy agreement (±1 kcal/mol) with the FPD results. The best agreement with the FPD results is predicted for the τ-HCTH functional with an average unsigned error of 8.3 kcal/mol.