Excited
state lifetime and steady state fluorescence of a series
of CdS quantum dots (QDs) with different sizes in toluene were quenched
by electron donor molecule N-methyl aniline (NMA).
Static quenching Collins–Kimball (SQCK) diffusion model enabled
convincing fittings to the steady-state and time-resolved data using
nearly a same set of parameters, only after considering the presence
of inherent quencher sites statistically distributed over the quantum
dot surface. Electron injection rate shows strong chemical driving
force dependency. QD with largest dimension (∼5.4 nm) used
in this study exhibits a slightly higher chemical driving force (−ΔG
0 = 0.80 eV) of electron
transfer as compared to that (−ΔG
0 = 0.79 eV) obtained for the smallest size QD
(∼3.8 nm). However, such a small change in driving force causes
nearly ∼3 times acceleration of the ET rate coefficient (k
0 = 8.30 × 109 M–1 s–1) within the larger size QD as compared to
that (k
0 = 2.74 × 109 M–1 s–1) observed in smaller size
QD. The time evolution of the sink term obtained from the Collins–Kimball
fitting of ET kinetics shows different regimes of the kinetics (static
and nonstationary).
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