Fractional electron transfer kinetics and a quantum breaking of ergodicity

Abstract

The dissipative curve-crossing problem provides a paradigm for electron-transfer (ET) processes in condensed media. It establishes the simplest conceptual test bed to study the influence of the medium's dynamics on ET kinetics both on the ensemble level, and on the level of single particles. Single electron description is particularly important for nanoscale systems. Slow medium's dynamics is capable to enslave ET and bring it on the ensemble level from a quantum regime of non-adiabatic tunneling to the classical adiabatic regime, where electrons just follow the nuclei rearrangements. This classical adiabatic textbook picture contradicts, however, in a very spectacular fashion to the statistics of single electron transitions, even in the Debye, memoryless media, named also Ohmic in the parlance of the famed spin-boson model. On the single particle level, ET remains always quantum and this was named a quantum breaking of ergodicity in the adiabatic ET regime. What happens in the case of subdiffusive, fractional, or sub-Ohmic medium's dynamics, which is featured by power-law decaying dynamical memory effects pertinent e.g. for protein macromolecules, and other viscoelastic media? Such a memory is vividly manifested by anomalous Cole-Cole dielectric response typical for such media. This is the question which is addressed in this work based both on precise numerics and analytical semi-classical theory. The ensemble theory remarkably agrees with the numerical dynamics of electronic populations, revealing a power law relaxation tail even in a deeply non-adiabatic electron transfer regime. However, a profound difference with the numerically accurate results emerges for the distribution of residence times in the electronic states, both on the ensemble level and on the level of single trajectories. Ergodicity is broken dynamically even in a more spectacular way than in the memoryless case.