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Communication: Predictive partial linearized path integral simulation of condensed phase electron transfer dynamics
20. A. R. Menzeleev, F. Bell, and T. F. Miller III, “Kinetically constrained ring polymer molecular dynamics for non-adiabatic chemical reactions” (unpublished).
40.In the limit of ωc → ∞ (here we found ωc = Ω is sufficient18), Eq. (6) can be re-expressed as a spin-boson model41 with a brownian spectral density: jbr(ω) = λ0Ω2ηω/[(ω2 − Ω2)2 + η2ω2], and . As a consistency check we verified that identical results are obtained with either model.
42.Here we choose the friction parameter in the range where the rate is invariant to changes of η (plateau region) according to Ref. 43.
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A partial linearized path integral approach is used to calculate the condensed phase electron transfer (ET) rate by directly evaluating the flux-flux/flux-side quantum time correlation functions. We demonstrate for a simple ET model that this approach can reliably capture the transition between non-adiabatic and adiabatic regimes as the electronic coupling is varied, while other commonly used semi-classical methods are less accurate over the broad range of electronic couplings considered. Further, we show that the approach reliably recovers the Marcus turnover as a function of thermodynamic driving force, giving highly accurate rates over four orders of magnitude from the normal to the inverted regimes. We also demonstrate that the approach yields accurate rate estimates over five orders of magnitude of inverse temperature. Finally, the approach outlined here accurately captures the electronic coherence in the flux-flux correlation function that is responsible for the decreased rate in the inverted regime.
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