  We use a numerically exact real-time path integral Monte Carlo scheme to
compute electron transfer dynamics between two redox sites within a spin-boson
approach. The case of asymmetric reactions is studied in detail in the least
understood crossover region between nonadiabatic and adiabatic electron
transfer. At intermediate-to-high temperature, we find good agreement with
standard Marcus theory, provided dynamical recrossing effects are captured. The
agreement with our data is practically perfect when temperature renormalization
is allowed. At low temperature we find peculiar electron transfer kinetics in
strongly asymmetric systems, characterized by rapid transient dynamics and
backflow to the donor.
