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Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal‐Field Models
Author(s) -
Gendron Frédéric,
PáezHernández Dayán,
Notter FrançoisPaul,
Pritchard Ben,
Bolvin Hélène,
Autschbach Jochen
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201305039
Subject(s) - wave function , chemistry , ab initio , atomic orbital , electronic structure , density functional theory , ground state , ab initio quantum chemistry methods , magnetization , linear combination of atomic orbitals , atomic physics , condensed matter physics , computational chemistry , physics , electron , quantum mechanics , magnetic field , molecule , basis set , organic chemistry
The electronic structure and magnetic properties of neptunyl(VI), NpO 2 2+ , and two neptunyl complexes, [NpO 2 (NO 3 ) 3 ] − and [NpO 2 Cl 4 ] 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 2 Cl 4 ] 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.