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Register a new userThe quantum solvation, adiabatic versus nonadiabatic, and Markovian versus non-Markovian nature of electron transfer rate processes
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In this work, we revisit the electron transfer rate theory, with particular interests in the distinct quantum solvation effect, and the characterizations of adiabatic/nonadiabatic and Markovian/non-Markovian rate processes. We first present a full account for the quantum solvation effect on the electron transfer in Debye solvents, addressed previously in J. Theore. & Comput. Chem. {bf 5}, 685 (2006). Distinct reaction mechanisms, including the quantum solvation-induced transitions from barrier-crossing to tunneling, and from barrierless to quantum barrier-crossing rate processes, are shown in the fast modulation or low viscosity regime. This regime is also found in favor of nonadiabatic rate processes. We further propose to use Kubos motional narrowing line shape function to describe the Markovian character of the reaction. It is found that a non-Markovian rate process is most likely to occur in a symmetric system in the fast modulation regime, where the electron transfer is dominant by tunneling due to the Fermi resonance.
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The study of quantum dynamics featuring memory effects has always been a topic of interest within the theory of open quantum system, which is concerned about providing useful conceptual and theoretical tools for the description of the reduced dynamics of a system interacting with an external environment. Definitions of non-Markovian processes have been introduced trying to capture the notion of memory effect by studying features of the quantum dynamical map providing the evolution of the system states, or changes in the distinguishability of the system states themselves. We introduce basic notions in the framework of open quantum systems, stressing in particular analogies and differences with models used for introducing modifications of quantum mechanics which should help in dealing with the measurement problem. We further discuss recent developments in the treatment of non-Markovian processes and their role in considering more general modifications of quantum mechanics.
The effect of solvation on the electron transfer (ET) rate processes is investigated on the basis of the exact theory constructed in J. Phys. Chem. B Vol. 110, (2006); quant-ph/0604071. The nature of solvation is studied in a close relation with the mechanism of ET processes. The resulting Kramers turnover and Marcus inversion characteristics are analyzed accordingly. The classical picture of solvation is found to be invalid when the solvent longitudinal relaxation time is short compared with the inverse temperature.
A general formalism is introduced to allow the steady state of non-Markovian processes on networks to be reduced to equivalent Markovian processes on the same substrates. The example of an epidemic spreading process is considered in detail, where all the non-Markovian aspects are shown to be captured within a single parameter, the effective infection rate. Remarkably, this result is independent of the topology of the underlying network, as demonstrated by numerical simulations on two-dimensional lattices and various types of random networks. Furthermore, an analytic approximation for the effective infection rate is introduced, which enables the calculation of the critical point and of the critical exponents for the non-Markovian dynamics.
Simulating complex processes can be intractable when memory effects are present, often necessitating approximations in the length or strength of the memory. However, quantum processes display distinct memory effects when probed differently, precluding memory approximations that are both universal and operational. Here, we show that it is nevertheless sensible to characterize the memory strength across a duration of time with respect to a sequence of probing instruments. We propose a notion of process recovery, leading to accurate predictions for any multi-time observable, with errors bounded by the memory strength. We then apply our framework to an exactly solvable non-Markovian model, highlighting the decay of memory for certain instruments that justify its truncation. Our formalism provides an unambiguous description of memory strength,paving the way for practical compression and recovery techniques pivotal to near-term quantum technologies.
We study the dynamics of a quantum system whose interaction with an environment is described by a collision model, i.e. the open dynamics is modelled through sequences of unitary interactions between the system and the individual constituents of the environment, termed ancillas, which are subsequently traced out. In this setting non-Markovianity is introduced by allowing for additional unitary interactions between the ancillas. For this model, we identify the relevant system-environment correlations that lead to a non-Markovian evolution. Through an equivalent picture of the open dynamics, we introduce the notion of memory depth where these correlations are established between the system and a suitably sized memory rendering the overall system+memory evolution Markovian. We extend our analysis to show that while most system-environment correlations are irrelevant for the dynamical characterization of the process, they generally play an important role in the thermodynamic description. Finally, we show that under an energy-preserving system-environment interaction, a non-monotonic time behaviour of the heat flux serves as an indicator of non-Markovian behaviour.
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