Three-dimensional models for the aqueous solvation structures of chloride, bromide, and iodide are reported. K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near edge (MXAN) analyses found well-defined single shell solvation spheres for bromide and iodide. However, dissolved chloride proved structurally distinct, with two solvation shells needed to explain its strikingly different X-ray absorption near edge structure (XANES) spectrum. Final solvation models were as follows: iodide, 8 water molecules at 3.60 ± 0.13 Å and bromide, 8 water molecules at 3.40 ± 0.14 Å, while chloride solvation included 7 water molecules at 3.15 ± 0.10 Å, and a second shell of 7 water molecules at 4.14 ± 0.30 Å. Each of the three derived solvation shells is approximately uniformly disposed about the halides, with no global asymmetry. Time-dependent density functional theory calculations simulating the chloride XANES spectra following from alternative solvation spheres revealed surprising sensitivity of the electronic state to 6-, 7-, or 8-coordination, implying a strongly bounded phase space for the correct structure during an MXAN fit. MXAN analysis further showed that the asymmetric solvation predicted from molecular dynamics simulations using halide polarization can play no significant part in bulk solvation. Classical molecular dynamics used to explore chloride solvation found a 7-water solvation shell at 3.12 (−0.04/+0.3) Å, supporting the experimental result. These experiments provide the first fully three-dimensional structures presenting to atomic resolution the aqueous solvation spheres of the larger halide ions.
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See supplementary material at http://dx.doi.org/10.1063/1.4959589 for information on (i) Normalized FT spectra of chloride, bromide, and iodide; (ii) EXAFS structural parameter search for iodide or bromide solvation; (iii) MXAN fits for bromide CN = 4, 6, 7, 8, or 10 water molecules; (iv) MXAN CN = 6 or 7 bromide solvation models; (v) EXAFS structural parameter search for chloride solvation; (vi) Cl K-edge EXAFS fit using 6, 7 (6,1), or 8 (6,1,1) oxygen scatterers; (vii) EXAFS metrics for homologous CN = 8 or 9 chloride models; (viii) EXAFS metrics for best CN = 7 or 8 chloride solvation models; (ix) MXAN CN = 6, 7, or 8 single shell fits to the chloride K-edge XAS; (x) MXAN CN = 6, 7, or 8 initial and final chloride single-shell models; (xi) MXAN fit to chloride XAS employing the two-shell solvation model; (xii) MD structural XAS using the HE, ME, or LEversions of the L-J potential; (xiii) Radial distribution and CNs of Cl–O for LE, HE, and MEL-J Potentials; (xiv) MD structural XAS using the GROMOS96 L-J potential; (xv) MD GROMOS96 L-J Cl–O RDF after the Rth filter; (xvi) MD rdfs, AMBER potential, SPC/E and TIP3P water models; (xvii) MD rdfs CHARMM potential, SPC/E, +ENCAD, TIP5P water models; (xviii) MD rdfs OPLS, CHARMM, GROMOS96,and AMBER potentials; (xix) MD rdfs GROMOS96 and polarization potentials; (xx) D-MXAN XANES from CHARMM potential and SPC/E water model; (xxi) D-MXAN XANES from CHARMM, +ENCAD shift and SPC/E; (xxii) D-MXAN XANES from CHARMM, +ENCAD shift and TIP5P; (xxiii) D-MXAN XANES from Gromacs polarization scheme; (xxiv) MD Scheme XANES Goodness of Fit; (xxv) EXAFS attenuation with mean back-scatterer displacement; (xxvi) Cl–H and Cl–O g(r)s from neutron diffraction. PDB file of each of the three final halide XAS solvation models: chloride, Chloride_14_water.pdb; bromide, Bromide_8_water.pdb; and iodide, Iodide_8_water.pdb.
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