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Covalent vs Electrostatic Interactions in Rare Earth Systems: A Comparative Study of U(III), U(IV), and U(V) and Nd(III) Bonding Properties by DFT and CAS-PT2 Approaches (dagger).

Vetere, Valentina; Maldivi, Pascale; Roos, Björn LU and Adamo, Carlo (2009) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 113(52). p.14760-14765
Abstract
A description of the electronic structure of F(3)UCO, F(3)NdCO, F(4)UCO, and F(5)UCO has been obtained by Complete Active Space second-order perturbation theory CASPT2 calculations using a relativistic effective core potential. These multiconfigurational calculations have been compared to the DFT description combined with a quasi-relativistic ZORA scalar approach. Geometries have been optimized for both levels of calculations and frequencies computed in the DFT formalism. The bonding properties of U(III) have been compared to those of Nd(III) and of higher oxidation states of U(IV,V). Both methodologies are consistent and show a decrease of the covalent character of the U-CO bonding with a higher oxidation state, U(IV) or U(V), as well as... (More)
A description of the electronic structure of F(3)UCO, F(3)NdCO, F(4)UCO, and F(5)UCO has been obtained by Complete Active Space second-order perturbation theory CASPT2 calculations using a relativistic effective core potential. These multiconfigurational calculations have been compared to the DFT description combined with a quasi-relativistic ZORA scalar approach. Geometries have been optimized for both levels of calculations and frequencies computed in the DFT formalism. The bonding properties of U(III) have been compared to those of Nd(III) and of higher oxidation states of U(IV,V). Both methodologies are consistent and show a decrease of the covalent character of the U-CO bonding with a higher oxidation state, U(IV) or U(V), as well as its absence for for the isoelectronic Nd(III) species. (Less)
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organization
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Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
113
issue
52
pages
14760 - 14765
publisher
The American Chemical Society
external identifiers
  • wos:000273263700073
  • pmid:19891466
  • scopus:73949085748
ISSN
1520-5215
DOI
10.1021/jp904889w
language
English
LU publication?
yes
id
aea1c675-a599-44f3-a636-7a6aeebd6d7f (old id 1512225)
date added to LUP
2009-12-01 08:09:21
date last changed
2017-08-27 04:07:33
@article{aea1c675-a599-44f3-a636-7a6aeebd6d7f,
  abstract     = {A description of the electronic structure of F(3)UCO, F(3)NdCO, F(4)UCO, and F(5)UCO has been obtained by Complete Active Space second-order perturbation theory CASPT2 calculations using a relativistic effective core potential. These multiconfigurational calculations have been compared to the DFT description combined with a quasi-relativistic ZORA scalar approach. Geometries have been optimized for both levels of calculations and frequencies computed in the DFT formalism. The bonding properties of U(III) have been compared to those of Nd(III) and of higher oxidation states of U(IV,V). Both methodologies are consistent and show a decrease of the covalent character of the U-CO bonding with a higher oxidation state, U(IV) or U(V), as well as its absence for for the isoelectronic Nd(III) species.},
  author       = {Vetere, Valentina and Maldivi, Pascale and Roos, Björn and Adamo, Carlo},
  issn         = {1520-5215},
  language     = {eng},
  number       = {52},
  pages        = {14760--14765},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Covalent vs Electrostatic Interactions in Rare Earth Systems: A Comparative Study of U(III), U(IV), and U(V) and Nd(III) Bonding Properties by DFT and CAS-PT2 Approaches (dagger).},
  url          = {http://dx.doi.org/10.1021/jp904889w},
  volume       = {113},
  year         = {2009},
}