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Title: Solvation structure of the halides from x-ray absorption spectroscopy

Abstract

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 tomore » 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.« less

Authors:
; ;  [1]; ;  [2];  [3];  [4];  [5];  [1];  [4]
  1. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025 (United States)
  2. Laboratori Nazionali di Frascati-INFN, P.O. Box 13, 00044 Frascati (Italy)
  3. Department of Chemistry, Stanford University, Stanford, California 94305 (United States)
  4. (United States)
  5. CINECA, SCAI—SuperComputing Applications and Innovation Department, Via dei Tizii 6, 00185 Roma (Italy)
Publication Date:
OSTI Identifier:
22679005
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 145; Journal Issue: 4; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; BROMIDES; CHLORIDES; DENSITY FUNCTIONAL METHOD; EXPERIMENTAL DATA; FINE STRUCTURE; IODIDES; IONS; MOLECULAR DYNAMICS METHOD; MOLECULES; SIMULATION; SOLVATION; SOLVENTS; SPHERICAL CONFIGURATION; TIME DEPENDENCE; X-RAY SPECTROSCOPY

Citation Formats

Antalek, Matthew, Hedman, Britt, Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu, Pace, Elisabetta, Benfatto, Maurizio, E-mail: Maurizio.Benfatto@lnf.infn.it, Hodgson, Keith O., SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025, Chillemi, Giovanni, E-mail: g.chillemi@cineca.it, Frank, Patrick, E-mail: pfrank@slac.stanford.edu, and Department of Chemistry, Stanford University, Stanford, California 94305. Solvation structure of the halides from x-ray absorption spectroscopy. United States: N. p., 2016. Web. doi:10.1063/1.4959589.
Antalek, Matthew, Hedman, Britt, Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu, Pace, Elisabetta, Benfatto, Maurizio, E-mail: Maurizio.Benfatto@lnf.infn.it, Hodgson, Keith O., SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025, Chillemi, Giovanni, E-mail: g.chillemi@cineca.it, Frank, Patrick, E-mail: pfrank@slac.stanford.edu, & Department of Chemistry, Stanford University, Stanford, California 94305. Solvation structure of the halides from x-ray absorption spectroscopy. United States. doi:10.1063/1.4959589.
Antalek, Matthew, Hedman, Britt, Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu, Pace, Elisabetta, Benfatto, Maurizio, E-mail: Maurizio.Benfatto@lnf.infn.it, Hodgson, Keith O., SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025, Chillemi, Giovanni, E-mail: g.chillemi@cineca.it, Frank, Patrick, E-mail: pfrank@slac.stanford.edu, and Department of Chemistry, Stanford University, Stanford, California 94305. Thu . "Solvation structure of the halides from x-ray absorption spectroscopy". United States. doi:10.1063/1.4959589.
@article{osti_22679005,
title = {Solvation structure of the halides from x-ray absorption spectroscopy},
author = {Antalek, Matthew and Hedman, Britt and Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu and Pace, Elisabetta and Benfatto, Maurizio, E-mail: Maurizio.Benfatto@lnf.infn.it and Hodgson, Keith O. and SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025 and Chillemi, Giovanni, E-mail: g.chillemi@cineca.it and Frank, Patrick, E-mail: pfrank@slac.stanford.edu and Department of Chemistry, Stanford University, Stanford, California 94305},
abstractNote = {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.},
doi = {10.1063/1.4959589},
journal = {Journal of Chemical Physics},
number = 4,
volume = 145,
place = {United States},
year = {Thu Jul 28 00:00:00 EDT 2016},
month = {Thu Jul 28 00:00:00 EDT 2016}
}