Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 113, Issue 6, Pages 1040-1048Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp807412c
Keywords
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Funding
- US National Science Foundation [CHE-0415457, CHE-0718755]
- Australian Research Council
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0718755] Funding Source: National Science Foundation
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This study explores how the electron transfer in a class of donor-bridge-acceptor (DBA) supermolecules is affected by the dynamical response of the solvent. These DBA molecules have a pendant group juxtaposed between the donor and acceptor groups (Figure 1). The pendant provides intermediate electronic coupling strengths of a few hundred wavenumbers by way of its nonbonded contacts with the donor and acceptor and it can be tuned by substituents added to the pendant. This design allows the measurement of electron transfer rates from a regime in which the mechanism is nonadiabatic to a regime in which the solvent friction modifies the rate substantially. The rate constants and mechanistic parameters are compared with the expectations of models for solvent dynamical effects on the reaction rate.
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