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Donor–bridge–acceptor structural fluctuations cause coupling values, HDA, to vary. When exchange among molecular conformations is much faster than the ET rate, ⟨HDA2⟩ enters the nonadiabatic rate expression in place of a single coupling value. The probability density for couplings, P(HDA), is determined by structures accessed.27,43,70 In the regime of slow exchange among conformations (kexch ≪ kET), nonexponential or gated kinetics may be measured.
