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The coordination of uranyl in water: A combined quantum chemical and molecular simulation study

Hagberg, Daniel LU ; Karlström, Gunnar LU ; Roos, Björn LU and Gagliardi, L (2005) In Journal of the American Chemical Society 127(41). p.14250-14256
Abstract
The coordination environment of uranyl in water has been studied using a combined quantum mechanical and molecular dynamics approach. Multiconfigurational wave function calculations have been performed to generate pair potentials between uranyl and water. The quantum chemically determined energies have been used to fit parameters in a polarizable force field with an added charge transfer term. Molecular dynamics simulations have been performed for the uranyl ion and up to 400 water molecules. The results show a uranyl ion with five water molecules coordinated in the equatorial plane. The U-O(H2O) distance is 2.40 angstrom, which is close to the experimental estimates. A second coordination shell starts at about 4.7 angstrom from the... (More)
The coordination environment of uranyl in water has been studied using a combined quantum mechanical and molecular dynamics approach. Multiconfigurational wave function calculations have been performed to generate pair potentials between uranyl and water. The quantum chemically determined energies have been used to fit parameters in a polarizable force field with an added charge transfer term. Molecular dynamics simulations have been performed for the uranyl ion and up to 400 water molecules. The results show a uranyl ion with five water molecules coordinated in the equatorial plane. The U-O(H2O) distance is 2.40 angstrom, which is close to the experimental estimates. A second coordination shell starts at about 4.7 angstrom from the uranium atom. No hydrogen bonding is found between the uranyl oxygens and water. Exchange of waters between the first and second solvation shell is found to occur through a path intermediate between association and interchange. This is the first fully ab initio determination of the solvation of the uranyl ion in water. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
127
issue
41
pages
14250 - 14256
publisher
The American Chemical Society
external identifiers
  • wos:000232605600048
  • scopus:26844509303
ISSN
1520-5126
DOI
10.1021/ja0526719
language
English
LU publication?
yes
id
ff414b14-0467-46a1-b343-52f8064a8bb1 (old id 152688)
date added to LUP
2007-07-17 10:33:51
date last changed
2017-11-19 04:11:12
@article{ff414b14-0467-46a1-b343-52f8064a8bb1,
  abstract     = {The coordination environment of uranyl in water has been studied using a combined quantum mechanical and molecular dynamics approach. Multiconfigurational wave function calculations have been performed to generate pair potentials between uranyl and water. The quantum chemically determined energies have been used to fit parameters in a polarizable force field with an added charge transfer term. Molecular dynamics simulations have been performed for the uranyl ion and up to 400 water molecules. The results show a uranyl ion with five water molecules coordinated in the equatorial plane. The U-O(H2O) distance is 2.40 angstrom, which is close to the experimental estimates. A second coordination shell starts at about 4.7 angstrom from the uranium atom. No hydrogen bonding is found between the uranyl oxygens and water. Exchange of waters between the first and second solvation shell is found to occur through a path intermediate between association and interchange. This is the first fully ab initio determination of the solvation of the uranyl ion in water.},
  author       = {Hagberg, Daniel and Karlström, Gunnar and Roos, Björn and Gagliardi, L},
  issn         = {1520-5126},
  language     = {eng},
  number       = {41},
  pages        = {14250--14256},
  publisher    = {The American Chemical Society},
  series       = {Journal of the American Chemical Society},
  title        = {The coordination of uranyl in water: A combined quantum chemical and molecular simulation study},
  url          = {http://dx.doi.org/10.1021/ja0526719},
  volume       = {127},
  year         = {2005},
}