TY - JOUR

T1 - Spin-orbit effects on the optical and magnetic properties of cerium (III) hexahalides

AU - Ferraro, Franklin

AU - Arratia-Pérez, Ramiro

N1 - Funding Information:
We thank Luis Seijo for sending us his published and unpublished work on these systems. We thank Fondecyt 1070345 , UNAB-DI 02-09/R and UNAB-DI-27-10/I for funding this work. FF thanks Conicyt for a graduate fellowship No. 63100014.

PY - 2011/3/24

Y1 - 2011/3/24

N2 - In this work we study the [CeX6]3-, X = Cl, Br, I octahedral complexes. The DFT geometry optimizations and the molecular properties calculations were performed using the PBE functional and TZ2P basis set through the use of the two-component ZORA Hamiltonian to include the scalar and spin-orbit relativistic effects. The optimized structures were used in the four-component SCF DSW code to calculate the molecular orbital energies and the paramagnetic resonance (giso and Ahfi) parameters. These results are in agreement with cerium chlorine-elpasolite (Cs 2NaCeCl6) experimental studies. Experimentally, the ground state span the Γ7u symmetry in octahedral geometry, and the excited states give rise to four "4f-4f" type transitions and three "4f-5d" type transitions. The correct descriptions of such transitions are only possible by calculations which include spin-orbit coupling effects, such as, the four-component Dirac equation or its two-component ZORA approximation. Such results confirm the need to include relativistic effects in the calculations of optical and magnetic properties in these lanthanide complexes. These results are in agreement with the spectrochemical series, in which the effect of the ligands follows the usual order: Cl- > Br- > I-.

AB - In this work we study the [CeX6]3-, X = Cl, Br, I octahedral complexes. The DFT geometry optimizations and the molecular properties calculations were performed using the PBE functional and TZ2P basis set through the use of the two-component ZORA Hamiltonian to include the scalar and spin-orbit relativistic effects. The optimized structures were used in the four-component SCF DSW code to calculate the molecular orbital energies and the paramagnetic resonance (giso and Ahfi) parameters. These results are in agreement with cerium chlorine-elpasolite (Cs 2NaCeCl6) experimental studies. Experimentally, the ground state span the Γ7u symmetry in octahedral geometry, and the excited states give rise to four "4f-4f" type transitions and three "4f-5d" type transitions. The correct descriptions of such transitions are only possible by calculations which include spin-orbit coupling effects, such as, the four-component Dirac equation or its two-component ZORA approximation. Such results confirm the need to include relativistic effects in the calculations of optical and magnetic properties in these lanthanide complexes. These results are in agreement with the spectrochemical series, in which the effect of the ligands follows the usual order: Cl- > Br- > I-.

KW - Lanthanide complexes

KW - Spin-orbit coupling

KW - Zora and Dirac Hamiltonians

UR - http://www.scopus.com/inward/record.url?scp=79952004902&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2010.12.020

DO - 10.1016/j.poly.2010.12.020

M3 - Article

AN - SCOPUS:79952004902

VL - 30

SP - 860

EP - 863

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

IS - 5

ER -