Invited Paper AC+MI-WeA3
First-Principle Calculations of Magnetic Properties of Actinide Complexes

Wednesday, November 9, 2016, 3:00 pm, Room 103C

The calculation of properties of open-shell 5f molecules is a challenge for the methods of quantum chemistry : these complexes have many low lying configurations, spin-orbit effects are important and correlation effects must be taken into account. The SO-CASPT2 method gives results that compare well to experimental data : it is a two-step wave function based method. The multiconfigurational nature of the wave functions is described by starting with a CASSCF calculation, correlation effects are calculated by 2nd order theory and spin-orbit effects are introduced in the very last step by a state interaction procedure.

We will show by several examples how calculations have become a complementary tool to the experimental data in order to get information about the nature and the magnetization of the ground and excited states.

1. calculation of EPR parameters : the ground state and excited states of actinyl complexes depend strongly on the nature of the equatorial ligands. All calculations are rationalized using a model based on crystal field theory. [1,2,3]

2. calculation of the susceptibility of aquo An(III), An(IV), An(V) and An(VI) cations and comparison to the LS coupling scheme. [4]

3. calculation of the pNMR shifts in the An(Et-DPC) ₃^3- series and comparison with the lanthanide series. The variation in temperature of this shift will be discussed.

[1] D. Paez Hernandez, H. Bolvin J. Electron. Spectrosc. Relat. Phenom. 194, 74 (2014).

[2] F. Gendron, D. Paez Hernandez, F. P. Notter, B. Pritchard, H. Bolvin, J. Autschbach Chem. Eur. J. 20, 7994 (2014).

[3] F. Gendron, B. Pritchard, H. Bolvin, J. Autschbach Inorg. Chem. 53, 8577 (2014).

[4] M. Autillo, L. Guerin, H. Bolvin, P. Moisy, C. Berthon Phys. Chem. Chem. Phys. 18, 6515 (2016).