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Large variations in the propensity of aqueous oxychlorine anions for the solution/vapor interface

Ottosson, Niklas ; Vacha, Robert ; Aziz, Emad F. ; Pokapanich, Wandared ; Eberhardt, Wolfgang ; Svensson, Svante ; Öhrwall, Gunnar LU orcid ; Jungwirth, Pavel ; Bjorneholm, Olle and Winter, Bernd (2009) In Journal of Chemical Physics 131(12).
Abstract
Core-level photoelectron spectroscopy measurements have been performed of aqueous solutions of NaCl codissolved with NaClOn (n=1-4). Each species has a distinct Cl 2p electron binding energy, which can be exploited for depth-profiling experiments to study the competition between Cl-and ClOn- anions for residing in the outermost layers of the solution/vapor interface. Strongest propensity for the surface is observed for n=4 (perchlorate), followed by n=3 (chlorate), n=2 (chlorite), n=0 (chloride), and n=1 (hypochlorite). Molecular dynamics simulations rationalize the greatest surface propensity of the most oxidized anions in terms of their larger size and polarizability. The anomalous behavior of hypochlorite, being less surface-active than... (More)
Core-level photoelectron spectroscopy measurements have been performed of aqueous solutions of NaCl codissolved with NaClOn (n=1-4). Each species has a distinct Cl 2p electron binding energy, which can be exploited for depth-profiling experiments to study the competition between Cl-and ClOn- anions for residing in the outermost layers of the solution/vapor interface. Strongest propensity for the surface is observed for n=4 (perchlorate), followed by n=3 (chlorate), n=2 (chlorite), n=0 (chloride), and n=1 (hypochlorite). Molecular dynamics simulations rationalize the greatest surface propensity of the most oxidized anions in terms of their larger size and polarizability. The anomalous behavior of hypochlorite, being less surface-active than chloride, although it is both larger and more polarizable, is suggested to arise from the charge asymmetry over the anion, increasing its efficiency for bulk solvation. (C) 2009 American Institute of Physics. [doi:10.1063/1.3236805] (Less)
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Contribution to journal
publication status
published
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in
Journal of Chemical Physics
volume
131
issue
12
publisher
American Institute of Physics (AIP)
external identifiers
  • wos:000270380300070
  • scopus:70349630070
  • pmid:19791911
ISSN
0021-9606
DOI
10.1063/1.3236805
language
English
LU publication?
yes
id
7509c685-9f28-48b9-b7eb-9fb1a62aca1b (old id 1489602)
date added to LUP
2016-04-01 11:59:07
date last changed
2021-09-15 01:55:00
@article{7509c685-9f28-48b9-b7eb-9fb1a62aca1b,
  abstract     = {Core-level photoelectron spectroscopy measurements have been performed of aqueous solutions of NaCl codissolved with NaClOn (n=1-4). Each species has a distinct Cl 2p electron binding energy, which can be exploited for depth-profiling experiments to study the competition between Cl-and ClOn- anions for residing in the outermost layers of the solution/vapor interface. Strongest propensity for the surface is observed for n=4 (perchlorate), followed by n=3 (chlorate), n=2 (chlorite), n=0 (chloride), and n=1 (hypochlorite). Molecular dynamics simulations rationalize the greatest surface propensity of the most oxidized anions in terms of their larger size and polarizability. The anomalous behavior of hypochlorite, being less surface-active than chloride, although it is both larger and more polarizable, is suggested to arise from the charge asymmetry over the anion, increasing its efficiency for bulk solvation. (C) 2009 American Institute of Physics. [doi:10.1063/1.3236805]},
  author       = {Ottosson, Niklas and Vacha, Robert and Aziz, Emad F. and Pokapanich, Wandared and Eberhardt, Wolfgang and Svensson, Svante and Öhrwall, Gunnar and Jungwirth, Pavel and Bjorneholm, Olle and Winter, Bernd},
  issn         = {0021-9606},
  language     = {eng},
  number       = {12},
  publisher    = {American Institute of Physics (AIP)},
  series       = {Journal of Chemical Physics},
  title        = {Large variations in the propensity of aqueous oxychlorine anions for the solution/vapor interface},
  url          = {http://dx.doi.org/10.1063/1.3236805},
  doi          = {10.1063/1.3236805},
  volume       = {131},
  year         = {2009},
}