Diffusion Assisted Bimolecular Electron Injection to CdS Quantum Dots: Existence of Different Regimes in Time Dependent Sink Term of Collins–Kimball Model

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 (−ΔG0 = 0.80 eV) of electron transfer as compared to that (−ΔG0 = 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 (k0 = 8.30 × 109 M–1 s–1) within the larger size QD as compared to that (k0 = 2.74 × 109 M–1 s–1) observed in smaller size QD. The time evolu...