Université de Fribourg

Electronic fine structure calculation of [Gd(DOTA)(H₂O)]⁻ using LF-DFT: The zero field splitting

Senn, Florian ; Helm, Lothar ; Borel, Alain ; Daul, Claude A.

In: Comptes Rendus Chimie, 2011, vol. 15, no. 2-3, p. 250-254

Zerfo field splitting plays an important role in determining the electron spin relaxation of Gd(III) in solution. We understand the ZFS as an effect depending on the f electron structure and treat it in the framework of ligand field-density functional theory (LF-DFT). We apply this theory to calculate the ZFS of [Gd(DOTA)(H₂O)]⁻ from first principles, having an insight concerning the...

Université de Fribourg

Computational analysis of tris(1,2-ethanediamine) cobalt(III) complex ion: calculation of the ⁵⁹Co shielding tensor using LF-DFT

Senn, Florian ; Zlatar, Matija ; Gruden-Pavlovic, Maja ; Daul, Claude

In: Monatshefte für Chemie - Chemical Monthly : an International Journal of Chemistry, 2011, vol. 142, no. 6, p. 593-597

The ligand-field density functional theory (LF-DFT) approach is employed for calculations of the ⁵⁹Co nuclear magnetic resonance (NMR) shielding tensor of all four diastereoisomers (λλλ, λλδ, λδδ, and δδδ) of tris(1,2-ethanediamine) cobalt(III) complex ion, [Co(en)₃]³⁺. The obtained values split into two groups according to the point group of the diastereoisomers. The...

Université de Fribourg

Calculation of ⁵⁹Co shielding tensor σ using LF–DFT

Senn, Florian ; Daul, Claude A.

In: Journal of Molecular Structure: THEOCHEM, 2010, p. -

⁵⁹Co NMR shielding tensor σ calculation using perturbation theory within the framework of Ligand Field–Density Functional Theory (LF–DFT) [1] is implemented for transition-metal complexes as an extension of the LF–DFT methodology. We give some first results for absolute and relative shielding tensors, which are in a good agreement with experimental results as well as with other...

Université de Fribourg

The giant magnetic anisotropy energy of Fe⁺ ions in SrCl₂

Garcia-Fernandez, Pablo ; Senn, Florian ; Daul, Claude A. ; Aramburu, Jose Antonio ; Barriuso, Maria Teresa ; Moreno, Miguel

In: Physical Chemistry Chemical Physics, 2009, vol. 11, p. 7545-7548

We show that values of the magnetic anisotropy energy (MAE), which are about two orders of magnitude larger than the usual ones for transition metal cations in insulators (∼0.01–1 cm⁻¹), can be found for the less common ion Fe⁺. In SrCl₂ : Fe⁺, the MAE is 93 cm⁻¹ when calculated using second-order perturbation multi-configurational calculations (CASPT2) while a similar value...