Elucidating the mechanism behind the stabilization of multi-charged metal cations in water: A case study of the electronic states of microhydrated Mg2+, Ca2+ and Al3+”

Journal Article · Mon Apr 21 04:00:00 EDT 2014 · Physical Chemistry Chemical Physics. PCCP, 16(15):6886-6892

DOI:https://doi.org/10.1039/C3CP53636J· OSTI ID:1129333

Miliordos, Evangelos; Xantheas, Sotiris S.

Metal atoms typically have second and higher ionization potentials (IPs) that are larger than the IP of water, resulting in the Coulombic explosion of the first few [M(H2O)n]+q (q ≥ 2) clusters as the M+ + (H2O)n + or MOH+ + H3O+(H2O)n energy levels are energetically more stable than the M2+ + (H2O)n ones for small n. We present a theoretical analysis of the various electronic states correlating with the above channels that are involved in the sequential hydration of the Ca2+, Mg2+ and Al3+ cations with up to six water molecules that, for the first time, quantifies their relative shift with the degree of solvation accounting for the observed stabilization of those multi-charged metal cations in an aqueous solution. *

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1129333
• Report Number(s): PNNL-SA-96264; KC0301020
• Journal Information: Physical Chemistry Chemical Physics. PCCP, 16(15):6886-6892, Journal Name: Physical Chemistry Chemical Physics. PCCP, 16(15):6886-6892
• Country of Publication: United States
• Language: English