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Register a new userInstanton formulation of Fermis golden rule in the Marcus inverted regime
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Fermis golden rule defines the transition rate between weakly coupled states and can thus be used to describe a multitude of molecular processes including electron-transfer reactions and light-matter interaction. However, it can only be calculated if the wave functions of all internal states are known, which is typically not the case in molecular systems. Marcus theory provides a closed-form expression for the rate constant, which is a classical limit of the golden rule, and indicates the existence of a normal regime and an inverted regime. Semiclassical instanton theory presents a more accurate approximation to the golden-rule rate including nuclear quantum effects such as tunnelling, which has so far been applicable to complex anharmonic systems in the normal regime only. In this paper we extend the instanton method to the inverted regime and study the properties of the periodic orbit, which describes the tunnelling mechanism via two imaginary-time trajectories, one of which now travels in negative imaginary time. It is known that tunnelling is particularly prevalent in the inverted regime, even at room temperature, and thus this method is expected to be useful in studying a wide range of molecular transitions occurring in this regime.
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Marcus-Levich-Jortner (MLJ) theory is one of the most commonly used methods for including nuclear quantum effects into the calculation of electron-transfer rates and for interpreting experimental data. It divides the molecular problem into a subsystem treated quantum-mechanically by Fermis golden rule and a solvent bath treated by classical Marcus theory. As an extension of this idea, we here present a reduced semiclassical instanton theory, which is a multiscale method for simulating quantum tunnelling of the subsystem in molecular detail in the presence of a harmonic bath. We demonstrate that instanton theory is typically significantly more accurate than the cumulant expansion or the semiclassical Franck-Condon sum, which can give orders-of-magnitude errors and in general do not obey detailed balance. As opposed to MLJ theory, which is based on wavefunctions, instanton theory is based on path integrals and thus does not require solutions of the Schrodinger equation, nor even global knowledge of the ground- and excited-state potentials within the subsystem. It can thus be efficiently applied to complex, anharmonic multidimensional subsystems without making further approximations. In addition to predicting accurate rates, instanton theory gives a high level of insight into the reaction mechanism by locating the dominant tunnelling pathway as well as providing information on the reactant and product vibrational states involved in the reaction and the activation energy in the bath similarly to what would be found with MLJ theory.
A study is made of the behavior of unstable states in simple models which nevertheless are realistic representations of situations occurring in nature. It is demonstrated that a non-exponential decay pattern will ultimately dominate decay due to a lower limit to the energy. The survival rate approaches zero faster than the inverse square of the time when the time goes to infinity.
We study heating dynamics in isolated quantum many-body systems driven periodically at high frequency and large amplitude. Combining the high-frequency expansion for the Floquet Hamiltonian with Fermis golden rule (FGR), we develop a master equation termed the Floquet FGR. Unlike the conventional one, the Floquet FGR correctly describes heating dynamics, including the prethermalization regime, even for strong drives, under which the Floquet Hamiltonian is significantly dressed, and nontrivial Floquet engineering is present. The Floquet FGR depends on system size only weakly, enabling us to analyze the thermodynamic limit with small-system calculations. Our results also indicate that, during heating, the system approximately stays in the thermal state for the Floquet Hamiltonian with a gradually rising temperature.
We discuss the decay of unstable states into a quasicontinuum using models of the effective Hamiltonian type. The goal is to show that exponential decay and the golden rule are exact in a suitable scaling limit, and that there is an associated renormalization group (RG) with these properties as a fixed point. The method is inspired by a limit theorem for infinitely divisible distributions in probability theory, where there is a RG with a Cauchy distribution, i.e. a Lorentz line shape, as a fixed point. Our method of solving for the spectrum is well known; it does not involve a perturbation expansion in the interaction, and needs no assumption of a weak interaction. We use random matrices for the interaction, and show that the ensemble fluctuations vanish in the scaling limit. Thus the limit is the same for every model in the ensemble with probability one.
Fermis golden rule is of great importance in quantum dynamics. However, in many textbooks on quantum mechanics, its contents and limitations are obscured by the approximations and arguments in the derivation, which are inevitable because of the generic setting considered. Here we propose to introduce it by an ideal model, in which the quasi-continuum band consists of equaldistant levels extending from $-infty $ to $+infty $, and each of them couples to the discrete level with the same strength. For this model, the transition probability in the first order perturbation approximation can be calculated analytically by invoking the Poisson summation formula. It turns out to be a emph{piecewise linear} function of time, demonstrating on one hand the key features of Fermis golden rule, and on the other hand that the rule breaks down beyond the emph{Heisenberg time}, even when the first order perturbation approximation itself is still valid.
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