Optical observation of the kinetics of thermalization between the 3P0 and 3P1 excited states of Pr3+ in symmetrical Pr3+–Gd3+ pairs in CsCdBr3

The time dependence of thermalization between the 3P0 and 3P1 electronic states of Pr3+ in symmetrical Pr3+–Gd3+ pairs in CsCdBr3, following pulsed laser excitation into either state, is reflected in the time dependence of the luminescence from both states. The 3P0 and 3P1 states achieve thermal equilibrium in the microsecond time domain over the temperature range of study (215–340 K). Because the 3P0–3P1 energy gap is larger than the phonon cutoff in CsCdBr3, thermalization occurs via multiphonon processes. A rate-equation model for the thermalization process is presented, and the temperature dependence of the rate constants for 3P1←3P0 multiphonon absorption and 3P1→3P0 multiphonon emission is reported from 215–340 K. In contrast to CsCdBr3, the analogous thermalization kinetics in Pr3+–Gd3+ pairs in isostructural CsMgCl3 is not discernable in the 3P0 and 3P1 luminescence, because thermalization is instantaneous within the time resolution of our experiments (∼20 ns). The difference in the thermalization kinetics in the two lattices is attributed to the difference in the number of phonons required to bridge the 3P0–3P1 energy gap.