Ab Initio Study of Energy Transfer Pathways in Dinuclear Lanthanide Complex of Europium(III) and Terbium(III) Ions

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 118; no. 47; pp. 11244 - 11252
• Main Authors: Romanova, Ksenia A, Freidzon, Alexandra Ya, Bagaturyants, Alexander A, Galyametdinov, Yury G
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 26.11.2014
• Subjects: Channels; Coordination compounds; Electronics; Energy transfer; Fragments; Lanthanides; Ligands; Mathematical analysis
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/jp509492e

An ab initio XMCQDPT2/CASSCF study of energy transfer processes in the dinuclear lanthanide complex [(Acac)3Eu­(μ-Bpym)­Tb­(Acac)3] (Acac is acetylacetonate, and Bpym is 2,2′-bipyrimidine) and a corresponding computational procedure are presented. Because ligands in lanthanide complexes weakly interact with each other, the large dinuclear complex bearing seven organic ligands is divided into fragments that reproduce the electrostatic effects of the ions on the electronic and geometrical structure of the ligands. The multireference XMCQDPT2/CASSCF approach is directly applied to these relatively small fragments with reasonable computational cost. The calculated energies of the singlet and triplet excited states agree well with the experiment. Based on the calculated energies, the energy level diagrams of the complex are constructed and intramolecular energy transfer channels are determined.