Evidence of the participation of electronic excited states in the mechanism of positronium formation in substitutional Tb(1-x)Eu(x)(dpm)3 solid solutions studied by optical and positron annihilation spectroscopies.

Positronium formation in the bimary molecular solid solutions Tb(1-x)Eu(x) (dpm)(3) (dpm = dipivaloylmethanate) has been investigated. A strong linear correlation between the (5)D(4) Tb(iii) energy level excited state lifetime and the positronium formation probability has been observed. This correlation indicates that the ligand-to-metal charge transfer LMCT states act in both luminescence quenching and positronium formation inhibition, as previously proposed. A kinetic mechanism is proposed to explain this correlation and shows that excited electronic states have a very important role in the positronium formation mechanism.

Intramolecular energy transfer through charge transfer state in lanthanide compounds: a theoretical approach.

A theoretical approach for the intramolecular energy transfer process involving the ligand-to-metal charge transfer (LMCT) state in lanthanide compounds is developed. Considering a two-electron interaction, both the direct Coulomb and exchange interactions are taken into account, leading to expressions from which selection rules may be derived and transfer rates may be calculated. These selection rules show that the direct Coulomb and exchange mechanisms are complementary, in the same way as obtained in previous works for the case of ligand-lanthanide ion energy transfer processes. An important result from numerical estimates is that the channel ligand-LMCT state is by far the dominant case, leading to transfer rates higher than for the channel lanthanide ion-LMCT state by several orders of magnitude. The analysis of the emission quantum yield as a function of the relative energy position of the LMCT state in a typical Eu(3+) compound allows the identification of two quenching regions, the most pronounced one occurring close to the lower ligand triplet level.

On the use of ligand field parameters in the study of coordinated water molecules in Eu3+ complexes.

A new methodology is proposed by which the number of coordinated water molecules, n, can be estimated in Eu(3+) complexes. It is based on a comparison between the theoretical and experimental Stark levels, the former being calculated by assuming that n varies from 0 to 4 and predicting the so-called ligand field parameters, . The methodology, initially developed in the study of the Eu(pya)(3).nH(2)O complex, has been applied successfully to beta-diketonate complexes of Eu(3+), for which crystallographic and luminescence data are available.