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Published online by Cambridge University Press: 11 May 2023
The rates of charge transfer and energy transfer are essential for understanding nanoscale phenomena and processes. Here we introduce the general conditions for the emergence of rate processes in quantum mechanics. We refer to the generic scenario in which a transition is induced between eigenstates of a given Hamiltonian by a weak perturbation. Analysis reveals that when the initial and final states are pure states, the transition rate is time-dependent and fails to reach a finite constant value. If, however, the final state is a mixed ensemble that is sufficiently wide and dense in energy, a rate constant emerges, given by Fermi’s Golden Rule (FGR). When the initial state is also mixed, for example, a thermal equilibrium state, a thermal rate constant is formulated in terms of transition rates between specific eigenstates, summed over the final eigenstates, and averaging over the thermal distribution of the initial eigenstates.
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