Europium Luminescence: Electronic Densities and Superdelocalizabilities for a Unique Adjustment of Theoretical Intensity Parameters.
We advance the concept that the charge factors of the simple overlap model and the polarizabilities of Judd-Ofelt theory for the luminescence of europium complexes can be effectively and uniquely modeled by perturbation theory on the semiempirical electronic wave function of the complex. With only three adjustable constants, we introduce expressions that relate: (i) the charge factors to electronic densities, and (ii) the polarizabilities to superdelocalizabilities that we derived specifically for this purpose. The three constants are then adjusted iteratively until the calculated intensity parameters, corresponding to the (5)D0→(7)F2 and (5)D0→(7)F4 transitions, converge to the experimentally determined ones. This adjustment yields a single unique set of only three constants per complex and semiempirical model used. From these constants, we then define a binary outcome acceptance attribute for the adjustment, and show that when the adjustment is acceptable, the predicted geometry is, in average, closer to the experimental one. An important consequence is that the terms of the intensity parameters related to dynamic coupling and electric dipole mechanisms will be unique. Hence, the important energy transfer rates will also be unique, leading to a single predicted intensity parameter for the (5)D0→(7)F6 transition.
Pople Computational Chemistry Laboratory, Departamento de Química, CCET, UFS, 49100-000, Aracaju, SE, Brazil.|Departamento de Química Fundamental, CCEN, UFPE, 50590-470, Recife, PE, Brazil.
José Diogo L
JD
Dutra
Departamento de Química Fundamental, CCEN, UFPE, 50590-470, Recife, PE, Brazil.
Nathalia B D
NB
Lima
Pople Computational Chemistry Laboratory, Departamento de Química, CCET, UFS, 49100-000, Aracaju, SE, Brazil.
Ricardo O
RO
Freire
Departamento de Química Fundamental, CCEN, UFPE, 50590-470, Recife, PE, Brazil.
Alfredo M
AM
Simas