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The solvent shell structure of aqueous iodide : X-ray absorption spectroscopy and classical, hybrid QM/MM and full quantum molecular dynamics simulations

Tavernelli, I.; Milne, C. J.; van der Veen, R. M.; D'Angelo, P.; Bressler, Ch; Chergui, M. and Pham, Van-Thai LU (2010) In Chemical Physics 371(1-3). p.24-29
Abstract

The L3 X-ray absorption spectrum of aqueous iodide is reported, and its EXAFS is compared to theoretical spectra reconstructed from the radial distribution function of the iodide hydration obtained from classical, hybrid Quantum Mechanics Molecular Mechanics, (QM/MM) and full quantum (density functional theory, DFT) molecular dynamics simulations. Since EXAFS is mainly sensitive to short distances around the iodide ion, it is a direct probe of the local solvation structure. The comparison shows that QM/MM simulations deliver a satisfactory description of the EXAFS signal, while nonpolarizable classical simulations are somewhat less satisfactory and DFT-based simulations perform poorly. We also identify a weak anisotropy of... (More)

The L3 X-ray absorption spectrum of aqueous iodide is reported, and its EXAFS is compared to theoretical spectra reconstructed from the radial distribution function of the iodide hydration obtained from classical, hybrid Quantum Mechanics Molecular Mechanics, (QM/MM) and full quantum (density functional theory, DFT) molecular dynamics simulations. Since EXAFS is mainly sensitive to short distances around the iodide ion, it is a direct probe of the local solvation structure. The comparison shows that QM/MM simulations deliver a satisfactory description of the EXAFS signal, while nonpolarizable classical simulations are somewhat less satisfactory and DFT-based simulations perform poorly. We also identify a weak anisotropy of the water solvation shell around iodide, which may be of importance in electron photoejection experiments.

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author
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Aqueous halides, DFT, EXAFS, Molecular dynamics, QM/MM, Solvation shell, X-ray absorption spectroscopy
in
Chemical Physics
volume
371
issue
1-3
pages
6 pages
publisher
Elsevier
external identifiers
  • scopus:77953231161
ISSN
0301-0104
DOI
10.1016/j.chemphys.2010.03.023
language
English
LU publication?
no
id
e3cee281-7f7f-402e-8359-ba7cb4abd356
date added to LUP
2019-06-30 09:56:24
date last changed
2019-08-06 03:23:16
@article{e3cee281-7f7f-402e-8359-ba7cb4abd356,
  abstract     = {<p>The L<sub>3</sub> X-ray absorption spectrum of aqueous iodide is reported, and its EXAFS is compared to theoretical spectra reconstructed from the radial distribution function of the iodide hydration obtained from classical, hybrid Quantum Mechanics Molecular Mechanics, (QM/MM) and full quantum (density functional theory, DFT) molecular dynamics simulations. Since EXAFS is mainly sensitive to short distances around the iodide ion, it is a direct probe of the local solvation structure. The comparison shows that QM/MM simulations deliver a satisfactory description of the EXAFS signal, while nonpolarizable classical simulations are somewhat less satisfactory and DFT-based simulations perform poorly. We also identify a weak anisotropy of the water solvation shell around iodide, which may be of importance in electron photoejection experiments.</p>},
  author       = {Tavernelli, I. and Milne, C. J. and van der Veen, R. M. and D'Angelo, P. and Bressler, Ch and Chergui, M. and Pham, Van-Thai},
  issn         = {0301-0104},
  keyword      = {Aqueous halides,DFT,EXAFS,Molecular dynamics,QM/MM,Solvation shell,X-ray absorption spectroscopy},
  language     = {eng},
  month        = {05},
  number       = {1-3},
  pages        = {24--29},
  publisher    = {Elsevier},
  series       = {Chemical Physics},
  title        = {The solvent shell structure of aqueous iodide : X-ray absorption spectroscopy and classical, hybrid QM/MM and full quantum molecular dynamics simulations},
  url          = {http://dx.doi.org/10.1016/j.chemphys.2010.03.023},
  volume       = {371},
  year         = {2010},
}