title: Semiempirical study of the electronic and optical properties of the Er(8-hydroxyquinolinate)3 complex.
abstract: We use a simple quantum chemical semiempirical procedure to study the electronic properties of organic-lanthanide complexes, taking as a model system Er(8-hydroxyquinolinate)3. Among the problems inherent to such a study is the fact that the lanthanide ion has never been parametrized in any of the standard semiempirical Hamiltonians. To overcome this difficulty, the lanthanide ion is replaced by a different but somewhat similar parametrized ion, or merely by a point charge. Good agreement with experiment, where available, is obtained, particularly in the former case. In fact, the electronic properties of the complex (apart from the emission properties) are seen to be scarcely affected by the nature of the lanthanide ion itself, but the core interactions between the metal ion and the ligand units play a relevant role, also in the calculation of the excitation energies. In particular, the ordering and separation of both singlet and triplet excited states are affected. The main conclusion is that to describe in detail the mechanism of the energy-transfer process occurring in the complex it is essential to take into account the geometry relaxation effects in the excited states.
authors.affiliation: INFM, INSTM e Dipartimento di Chimica e Chimica Industriale, Università di Genova, Via Dodecaneso 31, I-16146 Genova, Italy. massimo@chimica.unige.it
authors.forename: Massimo
authors.initials: M
authors.lastname: Ottonelli
authors.forename: Gaetano Michele Maurizio
authors.initials: GM
authors.lastname: Izzo
authors.forename: Fabio
authors.initials: F
authors.lastname: Rizzo
authors.forename: Gianfranco
authors.initials: G
authors.lastname: Musso
authors.forename: Giovanna
authors.initials: G
authors.lastname: Dellepiane
authors.forename: Riccardo
authors.initials: R
authors.lastname: Tubino