Magnetic properties and electronic structure of neptunyl(VI) complexes: Wavefunctions, orbitals, and crystal-field models

Frédéric Gendron, Dayán Páez-Hernández, François Paul Notter, Ben Pritchard, Hélène Bolvin, Jochen Autschbach

Resultado de la investigación: Article

53 Citas (Scopus)

Resumen

The electronic structure and magnetic properties of neptunyl(VI), NpO 2 2+, and two neptunyl complexes, [NpO2(NO 3)3]- and [NpO2Cl4] 2-, were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory (DFT), as well as crystal-field (CF) models with parameters extracted from the ab initio calculations. Natural orbitals for electron density and spin magnetization from wavefunctions including spin-orbit coupling were employed to analyze the connection between the electronic structure and magnetic properties, and to link the results from CF models to the ab initio data. Free complex ions and systems embedded in a crystal environment were studied. Of prime interest were the electron paramagnetic resonance g-factors and their relation to the complex geometry, ligand coordination, and nature of the nonbonding 5f orbitals. The g-factors were calculated for the ground and excited states. For [NpO 2Cl4]2-, a strong influence of the environment of the complex on its magnetic behavior was demonstrated. Kohn-Sham DFT with standard functionals can produce reasonable g-factors as long as the calculation converges to a solution resembling the electronic state of interest. However, this is not always straightforward. Making waves: The electronic structure and magnetic properties of neptunyl(VI), NpO2 2+, and two neptunyl complexes, [NpO2(NO3)3]- (see figure) and [NpO2Cl4]2-, were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory, as well as crystal-field models with parameters extracted from the ab initio calculations.

Idioma originalEnglish
Páginas (desde-hasta)7994-8011
Número de páginas18
PublicaciónChemistry - A European Journal
Volumen20
N.º26
DOI
EstadoPublished - 23 jun 2014

Huella dactilar

Wave functions
Electronic structure
Magnetic properties
Density functional theory
Crystals
Electronic states
Excited states
Embedded systems
Ground state
Carrier concentration
Paramagnetic resonance
Magnetization
Orbits
Ligands
Ions
Geometry

ASJC Scopus subject areas

  • Chemistry(all)

Citar esto

Gendron, Frédéric ; Páez-Hernández, Dayán ; Notter, François Paul ; Pritchard, Ben ; Bolvin, Hélène ; Autschbach, Jochen. / Magnetic properties and electronic structure of neptunyl(VI) complexes : Wavefunctions, orbitals, and crystal-field models. En: Chemistry - A European Journal. 2014 ; Vol. 20, N.º 26. pp. 7994-8011.
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abstract = "The electronic structure and magnetic properties of neptunyl(VI), NpO 2 2+, and two neptunyl complexes, [NpO2(NO 3)3]- and [NpO2Cl4] 2-, were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory (DFT), as well as crystal-field (CF) models with parameters extracted from the ab initio calculations. Natural orbitals for electron density and spin magnetization from wavefunctions including spin-orbit coupling were employed to analyze the connection between the electronic structure and magnetic properties, and to link the results from CF models to the ab initio data. Free complex ions and systems embedded in a crystal environment were studied. Of prime interest were the electron paramagnetic resonance g-factors and their relation to the complex geometry, ligand coordination, and nature of the nonbonding 5f orbitals. The g-factors were calculated for the ground and excited states. For [NpO 2Cl4]2-, a strong influence of the environment of the complex on its magnetic behavior was demonstrated. Kohn-Sham DFT with standard functionals can produce reasonable g-factors as long as the calculation converges to a solution resembling the electronic state of interest. However, this is not always straightforward. Making waves: The electronic structure and magnetic properties of neptunyl(VI), NpO2 2+, and two neptunyl complexes, [NpO2(NO3)3]- (see figure) and [NpO2Cl4]2-, were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory, as well as crystal-field models with parameters extracted from the ab initio calculations.",
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Magnetic properties and electronic structure of neptunyl(VI) complexes : Wavefunctions, orbitals, and crystal-field models. / Gendron, Frédéric; Páez-Hernández, Dayán; Notter, François Paul; Pritchard, Ben; Bolvin, Hélène; Autschbach, Jochen.

En: Chemistry - A European Journal, Vol. 20, N.º 26, 23.06.2014, p. 7994-8011.

Resultado de la investigación: Article

TY - JOUR

T1 - Magnetic properties and electronic structure of neptunyl(VI) complexes

T2 - Wavefunctions, orbitals, and crystal-field models

AU - Gendron, Frédéric

AU - Páez-Hernández, Dayán

AU - Notter, François Paul

AU - Pritchard, Ben

AU - Bolvin, Hélène

AU - Autschbach, Jochen

PY - 2014/6/23

Y1 - 2014/6/23

N2 - The electronic structure and magnetic properties of neptunyl(VI), NpO 2 2+, and two neptunyl complexes, [NpO2(NO 3)3]- and [NpO2Cl4] 2-, were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory (DFT), as well as crystal-field (CF) models with parameters extracted from the ab initio calculations. Natural orbitals for electron density and spin magnetization from wavefunctions including spin-orbit coupling were employed to analyze the connection between the electronic structure and magnetic properties, and to link the results from CF models to the ab initio data. Free complex ions and systems embedded in a crystal environment were studied. Of prime interest were the electron paramagnetic resonance g-factors and their relation to the complex geometry, ligand coordination, and nature of the nonbonding 5f orbitals. The g-factors were calculated for the ground and excited states. For [NpO 2Cl4]2-, a strong influence of the environment of the complex on its magnetic behavior was demonstrated. Kohn-Sham DFT with standard functionals can produce reasonable g-factors as long as the calculation converges to a solution resembling the electronic state of interest. However, this is not always straightforward. Making waves: The electronic structure and magnetic properties of neptunyl(VI), NpO2 2+, and two neptunyl complexes, [NpO2(NO3)3]- (see figure) and [NpO2Cl4]2-, were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory, as well as crystal-field models with parameters extracted from the ab initio calculations.

AB - The electronic structure and magnetic properties of neptunyl(VI), NpO 2 2+, and two neptunyl complexes, [NpO2(NO 3)3]- and [NpO2Cl4] 2-, were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory (DFT), as well as crystal-field (CF) models with parameters extracted from the ab initio calculations. Natural orbitals for electron density and spin magnetization from wavefunctions including spin-orbit coupling were employed to analyze the connection between the electronic structure and magnetic properties, and to link the results from CF models to the ab initio data. Free complex ions and systems embedded in a crystal environment were studied. Of prime interest were the electron paramagnetic resonance g-factors and their relation to the complex geometry, ligand coordination, and nature of the nonbonding 5f orbitals. The g-factors were calculated for the ground and excited states. For [NpO 2Cl4]2-, a strong influence of the environment of the complex on its magnetic behavior was demonstrated. Kohn-Sham DFT with standard functionals can produce reasonable g-factors as long as the calculation converges to a solution resembling the electronic state of interest. However, this is not always straightforward. Making waves: The electronic structure and magnetic properties of neptunyl(VI), NpO2 2+, and two neptunyl complexes, [NpO2(NO3)3]- (see figure) and [NpO2Cl4]2-, were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory, as well as crystal-field models with parameters extracted from the ab initio calculations.

KW - ab initio calculations

KW - actinides

KW - density functional calculations

KW - electronic structure

KW - magnetic properties

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DO - 10.1002/chem.201305039

M3 - Article

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VL - 20

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EP - 8011

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

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