Energy gap law in the solvent isotope effect on radiationless transitions of rare earth ions

Abstract

Data on the fluorescent yields of tervalent ions of Pr, Sm, Eu, Gd, Tb, Dy, and Tm in H2O and D2O, containing perchlorate ions, and isotope effects on the fluorescence are reported. The results are interpreted in terms of the mechanisms responsible for radiationless processes in solutions of rare earth ions [Y. Haas and G. Stein, J. Phys. Chem. 75, 3668 (1971); 76, 1093 (1972)]. It is shown that along the series of the closely related rare earth ions, all of which exhibit well shielded f−f electronic transitions, the results can be correlated in terms of a single variable: the energy gap between the lowest fluorescent and highest nonfluorescent level. For several rare earth ions, the matching of this gap by a single high energy (OH or OD) vibration of one solvent molecule is the decisive factor accounting for observed yields and isotope ratios.