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.

Solid Eu(III) complexes studied by positron annihilation, optical and Mössbauer spectroscopies: insights on the positronium formation mechanism.

In this work, positron annihilation lifetime (PALS), Doppler broadening annihilation radiation lineshape (DBARL), Mössbauer and optical spectroscopies measurements were performed in Eu(III) dipivaloylmetanate complex, Eu(dpm)(3), at 295 and 80 K. The Eu(dpm)(3) complex is not luminescent at 298 K and does not form positronium. On the other hand, it is highly luminescent at 80K, but still does not form positronium. The absence of positronium formation at 80K cannot be explained by a ligand/metal charge transfer process. We found strong evidences that the electronic delocalization does not occur at both temperatures. Despite the Mössbauer results being inconclusive regarding the Eu(III)/Eu(II) reduction hypothesis, previous results showing positronium formation in other Eu(III) complexes suggest that this process is not occurring. Thus, more studies are needed to explain the absence of positronium in Eu(III) complexes.