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Coordination of the neptunyl ion with carbonate ions and water: a theoretical study.

Gagliardi, Laura and Roos, Björn LU (2002) In Inorganic Chemistry 41(5). p.1315-1319
Abstract
The results of a study on the ground-state of monocarbonate, bicarbonate, and tricarbonate complexes of neptunyl using multiconfigurational second-order perturbation theory (CASSCF/CASPT2) are presented. The equilibrium geometries of the complexes corresponding to neptunium in the formal oxidation state (V) have been fully optimized at the CASPT2 level of theory in the presence of an aqueous environment modeled by a reaction field Hamiltonian with a spherical cavity. Some water molecules have been explicitly included in the calculation. This study is consistent with the hypothesis that the monocarbonate complex has a pentacoordinated structure with three water molecules in the first coordination shell and that the bicarbonate complex has a... (More)
The results of a study on the ground-state of monocarbonate, bicarbonate, and tricarbonate complexes of neptunyl using multiconfigurational second-order perturbation theory (CASSCF/CASPT2) are presented. The equilibrium geometries of the complexes corresponding to neptunium in the formal oxidation state (V) have been fully optimized at the CASPT2 level of theory in the presence of an aqueous environment modeled by a reaction field Hamiltonian with a spherical cavity. Some water molecules have been explicitly included in the calculation. This study is consistent with the hypothesis that the monocarbonate complex has a pentacoordinated structure with three water molecules in the first coordination shell and that the bicarbonate complex has a hexacoordinated structure, with two water molecules in the first coordination shell. The typical bond distances are in good agreement with experimental results. The tricarbonate complex was studied with explicit counterions, which resulted in somewhat longer Npminus signcarbonate bond distances than experiment indicates. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
41
issue
5
pages
1315 - 1319
publisher
The American Chemical Society
external identifiers
  • pmid:11874370
  • wos:000174259300040
  • scopus:0037060754
ISSN
1520-510X
DOI
10.1021/ic011076e
language
English
LU publication?
yes
id
c29c62b3-8924-40b9-8e8a-7c7e229676b7 (old id 106492)
date added to LUP
2007-07-17 09:51:03
date last changed
2017-12-10 03:43:12
@article{c29c62b3-8924-40b9-8e8a-7c7e229676b7,
  abstract     = {The results of a study on the ground-state of monocarbonate, bicarbonate, and tricarbonate complexes of neptunyl using multiconfigurational second-order perturbation theory (CASSCF/CASPT2) are presented. The equilibrium geometries of the complexes corresponding to neptunium in the formal oxidation state (V) have been fully optimized at the CASPT2 level of theory in the presence of an aqueous environment modeled by a reaction field Hamiltonian with a spherical cavity. Some water molecules have been explicitly included in the calculation. This study is consistent with the hypothesis that the monocarbonate complex has a pentacoordinated structure with three water molecules in the first coordination shell and that the bicarbonate complex has a hexacoordinated structure, with two water molecules in the first coordination shell. The typical bond distances are in good agreement with experimental results. The tricarbonate complex was studied with explicit counterions, which resulted in somewhat longer Npminus signcarbonate bond distances than experiment indicates.},
  author       = {Gagliardi, Laura and Roos, Björn},
  issn         = {1520-510X},
  language     = {eng},
  number       = {5},
  pages        = {1315--1319},
  publisher    = {The American Chemical Society},
  series       = {Inorganic Chemistry},
  title        = {Coordination of the neptunyl ion with carbonate ions and water: a theoretical study.},
  url          = {http://dx.doi.org/10.1021/ic011076e},
  volume       = {41},
  year         = {2002},
}