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| - Solvent Adiabaticity Effects on Ultrafast Electron Transfer in Viologen Charge TransferComplexes
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| - Charge recombination (CR) kinetics following photoinduced charge transfer are measured by optical transientabsorption for complexes of dimethyl viologen and diheptyl viologen with 4,4‘-biphenol (MVBP and HVBP)in methanol. Exponential time constants for MVBP and HVBP are 480 and 790 fs, respectively. Kineticdifferences cannot be rationalized with a standard equilibrium nonadiabatic rate formula using parametersobtained from linear absorption and resonance Raman measurements, which give nearly indistinguishableresults for the two complexes. Solvent relaxation times and adiabaticities of MVBP are calculated using afull solvation correlation function approach. This analysis suggests that the smaller CR rate of HVBP is dueto solvent reorganization differences, and is consistent with a greater adiabatic contribution for HVBP thanMVBP. We conjecture that interactions between the diheptyl aliphatic groups of HVBP and the local solventstructure are responsible for the CR differences.
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