Luminescence emission spectra and decay kinetics of Ce3+ in YAG were investigated as a function of temperature (300–800 K) under excitation in the long wavelength tail of the lowest 4f–5d absorption spectrum. Both the anti-Stokes and Stokes emission intensity were found to exhibit an unusual non-monotonic temperature dependence compared to those commonly excited in the absorption band, where luminescence intensity decreases monotonically with increasing temperature. This phenomenon is well explained by a phonon-assisted anti-Stokes excitation model with strong vibronic interaction. It reveals that the intensity enhancement of Ce3+ anti-Stokes and Stokes emission is caused by the anti-Stokes excitation efficiency. Excitation efficiency is enhanced with increasing temperature, and thermal ionization of the 5d electron into the conduction band remains as the quenching mechanism of Ce3+ anti-Stokes and Stokes luminescence at high temperatures.
Photo-induced electron transfer versus molecular structure of acceptors is investigated using ultrafast time-resolved transient grating spectroscopy. Typical laser dyes Rhodamine 101 (Rh101) and Rhodamine 6G (Rh6G) in electron donor solvent-aniline are adopted as the objects. The forward electron transfer time constant from aniline to the excited singlet state of two Rhodamine dyes and subsequent back electron transfer from two dyes to aniline are measured. The experimental results denote that Rh6G presents faster electron transfer rates with aniline in both forward electron transfer and back electron transfer processes. With chemical calculation and qualitative analysis, it is found that the flexible molecular geometry of Rh6G leads to stronger electron coupling with donor solvent and further gives rise to larger electron transfer rates.
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