Structure and Dynamics of Sulfate Ion in Aqueous SolutionAn ab initio QMCF MD Simulation and Large Angle X-ray Scattering Study

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Abstract
The hydrated sulfate ion has been characterized in aqueous solution in structural and dynamic aspects using ab initio quantum mechanical charge field (QMCF) molecular dynamics (MD) simulation and large angle X-ray scattering (LAXS) methods. The LAXS data show an average coordination number of the sulfate ion of up to 12 water molecules bound through hydrogen bonding, while the QMCF MD simulation displays a wide range of coordination numbers between 8 and 14 with an average value of ∼11. The Os···Ow distance cannot be distinguished from the Ow···Ow distance in the LAXS experiment; the weighted mean O···O distance is 2.880(10) Å. In the simulation, the Os···Ow and Ow···Ow distances are found to be very similar, namely, 2.86 and 2.84 Å, respectively. The S−Os bond and S···Ow distance have been determined by the LAXS experiment as 1.495(6) and 3.61(2) Å, respectively, indicating an average nearly tetrahedral S−Os···Ow angle. The ∼5% deviations of simulation distances (1.47 and 3.82 Å) from the experimental ones can probably be ascribed to the neglect of correlation energy in the quantum mechanical method. The mean residence time of water ligands at O atoms, 2.57 ps, is longer than that in pure water, 1.7 ps, characterizing the sulfate ion as a weak structure maker.

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