title: Ca2+ solvation as a function of p, T, and pH from ab initio simulation.
abstract: First principles molecular dynamics simulations have been carried out at various temperatures and pressures starting with either Ca(2+) or CaO in a reactive volume of 63 H(2)O molecules. In the case of aqueous Ca(2+), the ion is surrounded by six H(2)O molecules in the first hydration shell at 300 K/0.3 GPa, with rare exchange between first and second hydrations shells. At 900 K/0.9 GPa, the coordination number in the first hydration shell fluctuates between six and eight, the average being 7.0. CaO immediately reacts with the surrounding H(2)O molecules to form Ca(2+) + 2OH(-). The hydroxyl ions form transient Ca(OH)(+) and Ca(OH)(2) complexes and have a mean residence time in the first coordination shell of Ca(2+) of 6 ± 4 ps at 500 K and 3 ± 3 ps at 900 K, respectively. At 500 K/0.5 GPa, the time-averaged relative concentrations of the transient Ca(2+), Ca(OH)(+), and Ca(OH)(2) species are 14%, 55%, and 29%, while at 900 K/0.9 GPa, they are 2%, 34%, and 63%.
authors.affiliation: Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany.
authors.forename: Waheed A
authors.initials: WA
authors.lastname: Adeagbo
authors.forename: Nikos L
authors.initials: NL
authors.lastname: Doltsinis
authors.forename: Michael
authors.initials: M
authors.lastname: Burchard
authors.forename: Walter V
authors.initials: WV
authors.lastname: Maresch
authors.forename: Thomas
authors.initials: T
authors.lastname: Fockenberg
mesh_terms: D002118:Calcium / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D006878:Hydroxides / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D011312:Pressure; D012995:Solubility; D013696:Temperature; D014867:Water / Q000737:chemistry
chemical_list: D006878:Hydroxides; D014867:Water; C031356:hydroxide ion; D002118:Calcium