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Coherent interactions are prevalent in numerous photodriven processes, ranging from photosynthetic energy transfer to superexchange-mediated electron transfer, resulting in numerous studies aimed towards identifying and understanding these interactions. A key motivator of this interest is the non-statistical scaling laws that result from coherently traversing multiple pathways due to quantum interference. To that end, we employed ultrafast transient absorption spectroscopy to measure electron transfer in two donor-acceptor molecular systems comprising a p-(9-anthryl)-N,N-dimethylaniline chromophore/electron donor and either one or two equivalent naphthalene-1,8:4,5-bis(dicarboximide) electron acceptors at both ambient and cryogenic temperatures. The two-acceptor compound shows a statistical factor of 2.1  0.2 rate enhancement at room temperature and a non-statistical factor of 2.6  0.2 rate enhancement at cryogenic temperatures, suggesting correlated interactions between the two acceptors with the donor and with the bath modes. Comparing the charge recombination rates indicates that the electron is delocalized over both acceptors at low temperature but localized on a single acceptor at room temperature. These results highlight the importance of shielding the system from bath fluctuations to preserve and ultimately exploit the coherent interactions. 

The kinetics of model contaminant 4-chloronitrobenzene (4-ClNB) reduction by Fe( ii ) in aqueous suspensions containing either or both goethite (α-FeOOH) nanoparticles and kaolinite (Al 2 Si 2 O 5 (OH) 4 ) were quantified to elucidate the effects of nonreactive clay minerals on the attenuation of nitroaromatic groundwater contaminants by iron oxide nanoparticles. Increasing the amount of kaolinite in the presence of goethite decreased the reduction rate of 4-ClNB and competitive Fe( ii ) adsorption on kaolinite occurred. Cryogenic transmission and scanning electron microscopy (cryo-TEM and cryo-SEM) images did not reveal significant loss of accessible reactive surface area as a result of heteroaggregation. Sequential-spike batch reactors revealed that in the presence of kaolinite, 4-ClNB reduction rate decreased by more than a factor of three with extended reaction as a result of kaolinite dissolution and subsequent incorporation of Al and Si in goethite or on the goethite surface. The reactive sites residing on the {110} faces were comparatively more reactive in the presence of a large loading of kaolinite, resulting in shorter and wider goethite particles after reaction. These results elucidate the mechanisms by which nonreactive clays affect the reactions of Fe( ii )/iron oxides in groundwater systems and indicate that nonreactive clays are not passive components.