title: Solvation of magnesium dication: molecular dynamics simulation and vibrational spectroscopic study of magnesium chloride in aqueous solutions.
abstract: Magnesium dication plays many significant roles in biochemistry. While it is available to the environment from both ocean waters and mineral salts on land, its roles in environmental and atmospheric chemistry are still relatively unknown. Several pieces of experimental evidence suggest that contact ion pairing may not exist at ambient conditions in solutions of magnesium chloride up to saturation concentrations. This is not typical of most ions. There has been disagreement in the molecular dynamics literature concerning the existence of ion pairing in magnesium chloride solutions. Using a force field developed during this study, we show that contact ion pairing is not energetically favorable. Additionally, we present a concentration-dependent Raman spectroscopic study of the Mg-O(water) hexaaquo stretch that clearly supports the absence of ion pairing in MgCl(2) solutions, although a transition occurring in the spectrum between 0.06x and 0.09x suggests a change in solution structure. Finally, we compare experimental and calculated observables to validate our force field as well as two other commonly used magnesium force fields, and in the process show that ion pairing of magnesium clearly is not observed at higher concentrations in aqueous solutions of magnesium chloride, independent of the choice of magnesium force field, although some force fields give better agreement to experimental results than others.
authors.affiliation: Environmental Molecular Science Institute and Department of Chemistry, University of California, Irvine, California 92697, USA.
authors.forename: Karen M
authors.initials: KM
authors.lastname: Callahan
authors.forename: Nadia N
authors.initials: NN
authors.lastname: Casillas-Ituarte
authors.forename: Martina
authors.initials: M
authors.lastname: Roeselová
authors.forename: Heather C
authors.initials: HC
authors.lastname: Allen
authors.forename: Douglas J
authors.initials: DJ
authors.lastname: Tobias
mesh_terms: D015636:Magnesium Chloride / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015203:Reproducibility of Results; D012996:Solutions; D013059:Spectrum Analysis, Raman; D014732:Vibration; D014867:Water / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D012996:Solutions; D015636:Magnesium Chloride; D014867:Water