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Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics

Stochastically averaged master equation for a quantum-dynamic system interacting with a thermal bath

Elmar G. Petrov, V. I. Teslenko, Igor Goychuk

Published May 1, 1994• 34 citations
Publisher

Abstract

The methods of nonequilibrium density-matrix and coarse-temporal conception are used to obtain the kinetic equation for the parameters ${\ensuremath{\gamma}}_{\mathit{n}\mathit{m}}$(t)=Sp[\ensuremath{\rho}^(t)\ensuremath{\Vert}n〉〈m\ensuremath{\Vert}] of a quantum-dynamic system (QDS) interacting with a thermal bath and external stochastic field. It is important that the stochastic field is taken exactly into consideration. For diagonal QDS parameters ${\ensuremath{\gamma}}_{\mathit{n}\mathit{n}}$(t) this equation is reduced to the generalized Pauli equation (GPE) with stochastic time-dependent coefficients ${\mathit{w}}_{\mathit{n}\mathit{m}}$(t). Special attention is given to the procedure of averaging over stochastic processes. It is shown that after averaging over energy fluctuations affected by the stochastic field, in the first cumulant approximation in terms of stochastic processes ${\mathit{w}}_{\mathit{n}\mathit{m}}$(t), the GPE is transformed to the Pauli equation for the QDS state population ${\mathit{P}}_{\mathit{n}}$(t)=〈${\ensuremath{\gamma}}_{\mathit{n}\mathit{n}}$(t)${\mathrm{〉}}_{\mathit{f}}$. As an example, the relaxation behavior of a two-level system interacting with a dichotomous field (dichotomous Markovian process of kangaroo type) and a harmonic oscillator coupled with a thermal bath is considered. It is shown that the probability of relaxation transitions between energy levels may be changed by several orders of magnitude under the influence of the dichotomous field.

DOI
10.1103/physreve.49.3894

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The methods of nonequilibrium density-matrix and coarse-temporal conception are used to obtain the kinetic equation for the parameters \ensuremathγnm{\ensuremath{\gamma}}_{\mathit{n}\mathit{m}}\ensuremathγnm​(t)=Sp[\ensuremath{\rho}^(t)\ensuremath{\Vert}n〉〈m\ensuremath{\Vert}] of a quantum-dynamic system (QDS) interacting with a thermal bath and external stochastic field. It is important that the stochastic field is taken exactly into consideration. For diagonal QDS parameters \ensuremathγnn{\ensuremath{\gamma}}_{\mathit{n}\mathit{n}}\ensuremathγnn​(t) this equation is reduced to the generalized Pauli equation (GPE) with stochastic time-dependent coefficients wnm{\mathit{w}}_{\mathit{n}\mathit{m}}wnm​(t). Special attention is given to the procedure of averaging over stochastic processes. It is shown that after averaging over energy fluctuations affected by the stochastic field, in the first cumulant approximation in terms of stochastic processes wnm{\mathit{w}}_{\mathit{n}\mathit{m}}wnm​(t), the GPE is transformed to the Pauli equation for the QDS state population Pn{\mathit{P}}_{\mathit{n}}Pn​(t)=〈\ensuremathγnn{\ensuremath{\gamma}}_{\mathit{n}\mathit{n}}\ensuremathγnn​(t)〉f{\mathrm{〉}}_{\mathit{f}}〉f​. As an example, the relaxation behavior of a two-level system interacting with a dichotomous field (dichotomous Markovian process of kangaroo type) and a harmonic oscillator coupled with a thermal bath is considered. It is shown that the probability of relaxation transitions between energy levels may be changed by several orders of magnitude under the influence of the dichotomous field.
A master equation for a quantum system coupled to a heat bath with stochastically fluctuating energy levels is derived by making use of the ensemble averaging and the averaging with respect to a stochastic process in the bath. Relaxation terms are determined in the Born approximation with respect to the system-bath interaction and the damping parameters related to a relaxation kernel are specified. In parallel with the spectral strength of the bath, the damping parameters determine the transient times for the Markovian description creating the physical origin of the slippage [A. Suarez, R. Sibey, and I. Oppenheim, J. Chem. Phys. 97, 5101 (1992)]. The influence of energy fluctuations of the bath is analyzed for a two-level system including the solution of the corresponding non-Markovian equation for the level population difference. The conditions for the formation of Boltzmann's thermal ratio between steady-state populations are evaluated as well.
We obtain kinetic equations for the stochastically averaged reduced density matrix of a quantum system driven by a dichotomous Markovian process and weakly coupled to a quantum thermal bath. These kinetic equations are exact in arbitrary dichotomous perturbation and provide a unified description of both small and large correlation time limits, along with an intermediate case. As an example, the problem of a dissipative two-level system with a dichotomically modulated difference in eigenergies is considered.
The nonequilibrium density matrix technique is utilized to study the incoherent transfer of a quantum particle coupled to a fluctuating environment. The dynamics of the environment is assumed to split into two different types of molecular motions. The first type is associated with low-amplitude vibrations forming a thermal bath (TB). High-amplitude displacements of separated molecular groups define the second type and create stochastic fields for acting on the transferred particle. Specifying the TB by a set of harmonic oscillators and the stochastic fields by a dichotomic process averaged kinetic equations were derived. These equations enable us to construct a rate constants expressions and to find the steady-state populations for a quantum particle. Regimes of enhanced or reduced particle transfer are discussed in detail in relation to the characteristics of the stochastic field and the TB. \textcopyright{} 1996 The American Physical Society.
A large number of multifaceted quantum transport processes in molecular systems and physical nanosystems can be treated in terms of quantum relaxation processes which couple to one or several fluctuating environments. A thermal equilibrium environment can conveniently be modelled by a thermal bath of harmonic oscillators. An archetype situation provides a two-state dissipative quantum dynamics, commonly known under the label of a spin-boson dynamics. An interesting and nontrivial physical situation emerges, however, when the quantum dynamics evolves far away from thermal equilibrium. This occurs, for example, when a charge transferring medium possesses nonequilibrium degrees of freedom, or when a strong time-dependent control field is applied externally. Accordingly, certain parameters of underlying quantum subsystem acquire stochastic character. Herein, we review the general theoretical framework which is based on the method of projector operators, yielding the quantum master equations for systems that are exposed to strong external fields. This allows one to investigate on a common basis the influence of nonequilibrium fluctuations and periodic electrical fields on quantum transport processes. Most importantly, such strong fluctuating fields induce a whole variety of nonlinear and nonequilibrium phenomena. A characteristic feature of such dynamics is the absence of thermal (quantum) detailed balance.
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.