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Physical review. E

Quantum Kramers model: Corrections to the linear response theory for continuous bath spectrum

Ilya Rips

Published Jan 12, 2017• 0 citations
Publisher

Abstract

Decay of the metastable state is analyzed within the quantum Kramers model in the weak-to-intermediate dissipation regime. The decay kinetics in this regime is determined by energy exchange between the unstable mode and the stable modes of thermal bath. In our previous paper [Phys. Rev. A 42, 4427 (1990)PLRAAN1050-294710.1103/PhysRevA.42.4427], Grabert's perturbative approach to well dynamics in the case of the discrete bath [Phys. Rev. Lett. 61, 1683 (1988)PRLTAO0031-900710.1103/PhysRevLett.61.1683] has been extended to account for the second order terms in the classical equations of motion (EOM) for the stable modes. Account of the secular terms reduces EOM for the stable modes to those of the forced oscillator with the time-dependent frequency (TDF oscillator). Analytic expression for the characteristic function of energy loss of the unstable mode has been derived in terms of the generating function of the transition probabilities for the quantum forced TDF oscillator. In this paper, the approach is further developed and applied to the case of the continuous frequency spectrum of the bath. The spectral density functions of the bath of stable modes are expressed in terms of the dissipative properties (the friction function) of the original bath. They simplify considerably for the one-dimensional systems, when the density of phonon states is constant. Explicit expressions for the fourth order corrections to the linear response theory result for the characteristic function of the energy loss and its cumulants are obtained for the particular case of the cubic potential with Ohmic (Markovian) dissipation. The range of validity of the perturbative approach in this case is determined (γ/ω_{b}<0.26), which includes the turnover region. The dominant correction to the linear response theory result is associated with the "work function" and leads to reduction of the average energy loss and its dispersion. This reduction increases with the increasing dissipation strength (up to ∼10%) within the range of validity of the approach. We have also calculated corrections to the depopulation factor and the escape rate for the quantum and for the classical Kramers models. Results for the classical escape rate are in very good agreement with the numerical simulations for high barriers. The results can serve as an additional proof of the robustness and accuracy of the linear response theory.

DOI
10.1103/physreve.95.012119

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Decay of the metastable state is analyzed within the quantum Kramers model in the weak-to-intermediate dissipation regime. The decay kinetics in this regime is determined by energy exchange between the unstable mode and the stable modes of thermal bath. In our previous paper [Phys. Rev. A 42, 4427 (1990)PLRAAN1050-294710.1103/PhysRevA.42.4427], Grabert's perturbative approach to well dynamics in the case of the discrete bath [Phys. Rev. Lett. 61, 1683 (1988)PRLTAO0031-900710.1103/PhysRevLett.61.1683] has been extended to account for the second order terms in the classical equations of motion (EOM) for the stable modes. Account of the secular terms reduces EOM for the stable modes to those of the forced oscillator with the time-dependent frequency (TDF oscillator). Analytic expression for the characteristic function of energy loss of the unstable mode has been derived in terms of the generating function of the transition probabilities for the quantum forced TDF oscillator. In this paper, the approach is further developed and applied to the case of the continuous frequency spectrum of the bath. The spectral density functions of the bath of stable modes are expressed in terms of the dissipative properties (the friction function) of the original bath. They simplify considerably for the one-dimensional systems, when the density of phonon states is constant. Explicit expressions for the fourth order corrections to the linear response theory result for the characteristic function of the energy loss and its cumulants are obtained for the particular case of the cubic potential with Ohmic (Markovian) dissipation. The range of validity of the perturbative approach in this case is determined (γ/ω_{b}<0.26), which includes the turnover region. The dominant correction to the linear response theory result is associated with the "work function" and leads to reduction of the average energy loss and its dispersion. This reduction increases with the increasing dissipation strength (up to ∼10%) within the range of validity of the approach. We have also calculated corrections to the depopulation factor and the escape rate for the quantum and for the classical Kramers models. Results for the classical escape rate are in very good agreement with the numerical simulations for high barriers. The results can serve as an additional proof of the robustness and accuracy of the linear response theory.
Well dynamics within the quantum Kramers model is studied. The validity of the approach based on linear-response theory for the bath of normal modes is explored by including the second-order terms in the classical equations of motion (EOM) for the stable modes. The effect of nonsecular terms describing the linear interaction between the stable modes vanishes upon averaging over the distribution of initial positions and velocities of stable modes. By accounting for the secular terms, the classical EOM's for the stable modes are reduced to those of forced oscillator with time-dependent frequency. An exact expression for the transition probability kernel is derived using the known quantum-mechanical solution for the model. The time-reversal symmetry of EOM ensures that the kernel satisfies the detailed-balance condition. The corrections to the linear-response-theory results for the kernel and for the average energy loss and its dispersion are exponentially small for the high-frequency modes due to the slow (adiabatic) variation of the frequency. They are important in the case of the continuum spectrum of the bath, when the dominant contribution is due to the low-frequency modes. The results demonstrate the validity of the perturbative approach in the study of well dynamics.
The quantum-mechanical version of the Kramers turnover problem is considered. The multidimensional character of the problem is taken into account via transformation to normal modes. This eliminates the coupling to the bath near the barrier top allowing the use of a simple harmonic transmission coefficient for the barrier dynamics. The well dynamics is described by a continuum form of a master equation for the energy in the unstable normal mode. Within first-order perturbation theory, the equations of motion for the stable normal modes have the form of a forced oscillator. The transition probability kernel is found using the known solution for the quantum forced oscillator problem. An expression for the quantum escape rate is derived. It encompasses all previously known limiting results in the thermally activated tunneling regime. The depopulation factor, which accounts for the nonequilibrium energy distribution is evaluated. The quantum transition probability kernel is broader than the classical and is skewed towards lower energies. Interplay between these two effects, together with a positive tunneling contribution, determines the relative magnitude of the quantum rate compared to the classical one. The theory is valid for arbitrary dissipation. Its use is illustrated for the case of a cubic potential with Ohmic (Markovian) dissipation.
Using a generalized version of Langer's "imaginary part of the free energy" method the quantum decay rate Γ = A exp (−B) of a metastable ohmic oscillator — with harmonic frequency ω0 and quantum friction coefficient α — is studied for an almost symmetric barrier and a "free" exit space, involving an "inflection scattering" center. The unstable anomalous fluctuation mode (of the "breathing bounce" configuration in the partition function) is analytically continued in a fully "dynamical" manner. At zero friction and zero temperature the result for Γ agrees with the escape rate found from the pertinent Schrodinger equation by means of an extended WKB "outgoing waves" analysis. At slightly elevated temperatures — removing the earlier restrictions 12B exp (− ħω0/2k B T) → 0 and 2πk B T/ħω0 → 0 arising from the "two-state" and "sudden-flip" approximations — in the weak quantum damping regime (α ≲ 1) the decay rate shows a characteristic transition from quantal to thermal dependence on the bias energy ε. In the strong quantum damping regime (α ≳ 1) this dependence is always thermal while — in that case — at zero bias the oscillator becomes "dissipatively frozen" at zero temperature.
The motion of a free quantum particle in a thermal environment is usually described by the quantum Langevin equation, where the effect of the bath is encoded through a dissipative and a noise term, related to each other via the fluctuation dissipation theorem. The quantum Langevin equation can be derived starting from a microscopic model of the thermal bath as an infinite collection of harmonic oscillators prepared in an initial equilibrium state. The spectral properties of the bath oscillators and their coupling to the particle determine the specific form of the dissipation and noise. Here we investigate in detail the well-known Rubin bath model, which consists of a one-dimensional harmonic chain with the boundary bath particle coupled to the Brownian particle. We show how in the limit of infinite bath bandwidth, we get the Drude model, and a second limit of infinite system-bath coupling gives the Ohmic model. A detailed analysis of relevant equilibrium correlation functions, such as the mean squared displacement, velocity autocorrelation functions, and response function are presented, with the aim of understanding the various temporal regimes. In particular, we discuss the quantum-to-classical crossover time scales where the mean square displacement changes from a ∼lnt to a ∼t dependence. We relate our study to recent work using linear response theory to understand quantum Brownian motion.
Exact expressions are derived for the intermediate scattering function (ISF) of a quantum particle diffusing in a harmonic potential and linearly coupled to a harmonic bath. The results are valid for arbitrary strength and spectral density of the coupling. The general, exact non-Markovian result is expressed in terms of the classical velocity autocorrelation function, which represents an accumulated phase during a scattering event. The imaginary part of the exponent of the ISF is proportional to the accumulated phase, which is an antisymmetric function of the correlation time ttt. The expressions extend previous results given in the quantum Langevin framework where the classical response of the bath was taken as Markovian. For a special case of non-Markovian friction, where the friction kernel decays exponentially in time rather than instantaneously, we provide exact results relating to unconfined quantum diffusion, and identify general features that allow insight to be exported to more complex examples. The accumulated phase as a function of the ttt has a universal gradient at the origin, depending only on the mass of the diffusing system particle. At large ttt the accumulated phase reaches a constant limit that depends only on the classical diffusion coefficient and is therefore independent of the detailed memory properties of the friction kernel. Non-Markovian properties of the friction kernel are encoded in the details of how the accumulated phase switches from its $t\ensuremath{\rightarrow}\ensuremath{-}\ensuremath{\infty}$ to its $t\ensuremath{\rightarrow}+\ensuremath{\infty}$ limit, subject to the constraint of the universal gradient. When memory effects are significant, the transition from one limit to the other becomes nonmonotonic, owing to oscillations in the classical velocity autocorrelation. The result is interpreted in terms of a solvent caging effect, in which slowly fluctuating bath modes create transient wells for the system particle.
We use the “generalized hierarchical equation of motion” proposed in Paper I [C.-Y. Hsieh and J. Cao, J. Chem. Phys. 148, 014103 (2018)] to study decoherence in a system coupled to a spin bath. The present methodology allows a systematic incorporation of higher-order anharmonic effects of the bath in dynamical calculations. We investigate the leading order corrections to the linear response approximations for spin bath models. Two kinds of spin-based environments are considered: (1) a bath of spins discretized from a continuous spectral density and (2) a bath of localized nuclear or electron spins. The main difference resides with how the bath frequency and the system-bath coupling parameters are distributed in an environment. When discretized from a continuous spectral density, the system-bath coupling typically scales as ∼1/NB where NB is the number of bath spins. This scaling suppresses the non-Gaussian characteristics of the spin bath and justifies the linear response approximations in the thermodynamic limit. For the nuclear/electron spin bath models, system-bath couplings are directly deduced from spin-spin interactions and do not necessarily obey the 1/NB scaling. It is not always possible to justify the linear response approximations in this case. Furthermore, if the spin-spin Hamiltonian is highly symmetrical, there exist additional constraints that generate highly non-Markovian and persistent dynamics that is beyond the linear response treatments.