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Physical Review A

Quantum Kramers model: Well dynamics beyond the linear-response theory

Ilya Rips

Published Oct 1, 1990• 6 citations
Publisher

Abstract

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.

DOI
10.1103/physreva.42.4427

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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.
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.
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.
We study the dynamics of relaxation and thermalization in an exactly solvable model of a particle interacting with a harmonic oscillator bath. Our goal is to understand the effects of non-Markovian processes on the relaxational dynamics and to compare the exact evolution of the distribution function with approximate Markovian and non-Markovian quantum kinetics. There are two different cases that are studied in detail: (i) a quasiparticle (resonance) when the renormalized frequency of the particle is above the frequency threshold of the bath and (ii) a stable renormalized "particle" state below this threshold. The time evolution of the occupation number for the particle is evaluated exactly using different approaches that yield to complementary insights. The exact solution allows us to investigate the concept of the formation time of a quasiparticle and to study the difference between the relaxation of the distribution of bare particles and that of quasiparticles. For the case of quasiparticles, the exact occupation number asymptotically tends to a statistical equilibrium distribution that differs from a simple Bose-Einstein form as a result of off-shell processes whereas in the stable particle case, the distribution of particles does not thermalize with the bath. We derive a non-Markovian quantum kinetic equation which resums the perturbative series and includes off-shell effects. A Markovian approximation that includes off-shell contributions and the usual Boltzmann equation (energy conserving) are obtained from the quantum kinetic equation in the limit of wide separation of time scales upon different coarse-graining assumptions. The relaxational dynamics predicted by the non-Markovian, Markovian, and Boltzmann approximations are compared to the exact result. The Boltzmann approach is seen to fail in the case of wide resonances and when threshold and renormalization effects are important.
A fully classical limit of the recently published quantum-classical approximation [A. A. Neufeld, J. Chem. Phys. 119, 2488 (2003)] is obtained and analyzed. The resulting kinetic equations are capable of describing the evolution of an open system on the entire time axis, including the short-time non-Markovian stage, and are valid beyond linear response regime. We have shown, that proceeding to the classical mechanics limit we restrict the class of allowed correlations between an open system and a canonical bath, so that the initial conditions and the relaxation operator has to be appropriately modified (projected). Disregard of the projection may lead to unphysical behavior, since mechanism of the decay of some correlations is essentially of quantum-mechanical nature, and is not correctly described by classical mechanics. The projection (quantum correction to the kinetics) is particularly important for the non-Markovian regime of relaxation towards canonical equilibrium. The conformity of the developed method to the conventional approaches is demonstrated using a model of Brownian motion (heavy particle in the bath of light ones), for which the obtained non-Markovian equations are reduced to the standard Fokker-Planck equation in phase space.
A quantum dissipation theory is constructed with the system–bath interaction being treated rigorously at the second-order cumulant level for both reduced dynamics and initial canonical boundary condition. The theory is valid for arbitrary bath correlation functions and time-dependent external driving fields, and satisfies correlated detailed-balance relation at any temperatures. The general formulation assumes a particularly simple form in driven Brownian oscillator systems in which the correlated driving-dissipation effects can be accounted for exactly in terms of local-field correction. Remarks on a class of widely used phenomenological quantum master equations that neglects the bath dispersion-induced dissipation are also made in contact with the present theory.
We investigate the difference between a quantum and classical bath within the Caldeira-Leggett model for dissipative quantum dynamics.It is well known that a Markovian equation of motion for the reduced dynamics can be derived by taking the classical approximation of the harmonic bath correlation function.However, such approximation is only valid at high temperatures, and it is necessary to include the non-Markovian effect of the quantum bath in more general cases.We show that the equation of motion derived for the classical bath can be extended to the exact quantum one, by simply adding a real stochastic process to take account of the difference between the quantum and classical bath correlation functions.Numerical examples in calculating electron and excitation energy transfer dynamics, as well as absorption spectra of molecular aggregates indicate that the proposed method is a valid approach to extend the existing theories to include the quantum effect of the harmonic bath.The possibility of applying a similar idea to account for the difference between zero and high temperature quantum dissipative dynamics is discussed.