Reevaluating the effects of reorganization energy on electron transfer rate for quantum dot-molecular acceptor...

The electron transfer (ET) rate in quantum dot (QD)-molecular acceptor systems is dependent upon system reorganization energy (RE, λ), which comprises contributions from solvent (λ₀) and reactants (λ_i). However, to date, the effect of λ_i on ET rate has been largely ignored. Herein, the ET from CdSe/ZnS QDs to 1-chloroanthraquinone (1-CAQ) in different solvents was investigated using ultrafast transient absorption spectroscopy as a means to evaluate the effect of λ_i on ET rate. The results revealed that ET rate is strongly solvent dependent. Amazingly, the ET rate in carbon disulfide is 300-times higher than that in n-dodecane. Theoretical calculations indicated that the λ_i contribution from 1-CAQ alone accounts for a large proportion of system RE and varies greatly in different solvents. Furthermore, the ET rate increases first and, then, decreases with the λ value in different solvents. This trend was interpreted consistently in terms of Marcus theory by adding λ_i to λ for different solvents. Thus, our present work demonstrates that the RE of the acceptor molecule has a non-negligible effect on ET rate, providing new insight into the mechanisms of ET process and for the development of QD-based devices.