The Redfield quantum master equation is widely used to study the dynamics of interacting sub-systems that are weakly coupled to baths. Redfield dynamics under secular approximation preserves positivity of the reduced density operator and thermalizes the system into a Gibbs state at equilibrium. Long-time effects arising from non-secular terms are often neglected, but depending on the system spectrum and relative bath couplings, non-secular contributions are shown here to drive the system into a non-Gibbs state. For two strongly interacting quantum oscillators with independent baths at equal temperature, we analyze the microscopic origin of the deviations from Gibbs statistics. Provided that the oscillators are unequally damped by their baths, we show that steady state occupation numbers can significantly deviate from a Boltzmann distribution due to an excitation flux driven by bath-induced coherences between nearly-degenerate oscillator levels. Conditions for the recovery of thermal Gibbs statistics are discussed and experimental signatures suggested.
The Redfield quantum master equation is widely used to study the dynamics of interacting sub-systems that are weakly coupled to baths. Redfield dynamics under secular approximation preserves positivity of the reduced density operator and thermalizes the system into a Gibbs state at equilibrium. Long-time effects arising from non-secular terms are often neglected, but depending on the system spectrum and relative bath couplings, non-secular contributions are shown here to drive the system into a non-Gibbs state. For two strongly interacting quantum oscillators with independent baths at equal temperature, we analyze the microscopic origin of the deviations from Gibbs statistics. Provided that the oscillators are unequally damped by their baths, we show that steady state occupation numbers can significantly deviate from a Boltzmann distribution due to an excitation flux driven by bath-induced coherences between nearly-degenerate oscillator levels. Conditions for the recovery of thermal Gibbs statistics are discussed and experimental signatures suggested.
The Lindblad form guarantees complete positivity of a Markovian quantum master equation (QME). However, its microscopic derivation for a quantum system weakly interacting with a thermal bath requires several approximations, which may result in inaccuracies in the QME. Recently, various Lindbladian QMEs were derived without resorting to the secular approximation from the Redfield equation which does not guarantee the complete positivity. Here we explicitly calculate, in a perturbative manner, the equilibrium steady states of these Lindbladian QMEs. We compare the results with the steady state of the Redfield equation obtained from an analytic continuation method, which coincides with the so-called mean force Gibbs (MFG) state. The MFG state is obtained by integrating out the bath degrees of freedom for the Gibbs state of the total Hamiltonian. We explicitly show that the steady states of the Lindbladian QMEs are different from the MFG state. Our results indicate that manipulations of the Redfield equation needed to enforce complete positivity of a QME drives its steady state away from the MFG state. We also find that, in the high-temperature regime, both the steady states of the Lindbladian QMEs and MFG state reduce to the same Gibbs state of a system Hamiltonian under certain conditions.
We present a systematic thermodynamic analysis of nonsecular GKLS master equations. When some energy transitions in the system are comparable with the dissipative rate, the secular approximation is not valid, and the positivity of the dynamics must be ensured via other approximations. The dynamics then presents features reminiscent from strong coupling to the environment: e.g. the equilibrium state with an environment at thermal equilibrium is not a Gibbs state of the local system Hamiltonian and the dynamics couples energy coherences and populations. Nonetheless, we build a unified, consistent thermodynamic framework for those dynamics. We focus on two approximations beyond the full secular approximation (the local and the more accurate geometric-arithmetic approximations), and then employ systematic perturbation theory on microscopic expressions for the first and second law of thermodynamics which relate irreversibility to the increase of system-environment correlations. We show that, in spite of the weak system-bath coupling, the system-bath interaction energy participates to the energy balance, and is directly linked to the Lamb-shift Hamiltonian. We compare this microscopic entropy production with the definition based on the contractivity of the reduced system dynamics (Spohn inequality). We show that, unlike for secular master equations, the two entropy production rates differ because of the presence of non-vanishing stationary coherences in the energy eigenbasis. However, in the case of a single thermal bath, the difference is purely transient, and no work can be cyclically extracted from the steady-state despite its non-Gibbs form. Finally, we illustrate our results with simple examples, clarifying and completing the thermodynamic picture of Markovian dynamics in the quantum regime.
In various fields from quantum physics to biology, the open quantum dynamics of a system consisting of interacting subsystems emphasizes its fundamental functionality. The local approach, deriving a dissipator in a master equation by ignoring the inter-subsystem interaction, has been widely used to describe the reduced dynamics due to its robustness to keep the positivity of a density operator. However, one critique is that a stationary state obtained by the approach in the limit of weak system-environment coupling is written in the form of the Gibbs state for the partial Hamiltonian by excluding the inter-subsystem interaction from the total one of the relevant system. As an alternative, the global approach, deriving a dissipator with including the inter-subsystem interaction, under the Born--Markov and secular approximations has attracted much attention, and there is debate concerning its violation of positivity in the short-term region and/or limited parameter region for the Bohr frequencies of the subsystems. In this study, we present a formalism that leads to the time-convolutionless (time-local) master equation obtained by extending the global approach beyond the Born-Markov and secular approximations. We apply it to the excitation energy transfer between interacting sites in which only the terminal site weakly interacts with a bosonic environment of finite temperature in a manner beyond the rotating-wave approximation. We find that the formulation (1) gives the short-time behavior while preserving positivity, (2) shows the oscillatory features that the secular approximation would obscure, and (3) leads to a stationary state very near to the Gibbs state for the total Hamiltonian of the relevant system.
We study the reduced dynamics of a pair of nondegenerate oscillators coupled collectively to a thermal bath. The model is related to the trilinear boson model where the idler mode is promoted to a field. Due to nonlinear coupling, the Markovian master equation for the pair of oscillators admits non-Gaussian equilibrium states, where the modes distribute according to the Bose-Einstein statistics. These states are metastable before the nonlinear coupling is taken over by linear coupling between the individual oscillators and the field. The Gibbs state for the individual modes lies in the subspace with infinite occupation quantum number. We present the time evolution of a few states to illustrate the behaviors of the system.
In various fields from quantum physics to biology, the open quantum dynamics of a system consisting of interacting subsystems emphasizes its fundamental functionality. The local approach, deriving a dissipator in a master equation by ignoring the intersubsystem interaction, has been widely used to describe the reduced dynamics due to its robustness to keep the positivity of a density operator. However, one critique is that a stationary state obtained by the approach in the limit of weak system-environment coupling is written in the form of the Gibbs state for the partial Hamiltonian by excluding the intersubsystem interaction from the total one of the relevant system. As an alternative, the global approach, deriving a dissipator with including the intersubsystem interaction, under the Born-Markov and secular approximations has attracted much attention, and there is debate concerning its violation of positivity in the short-time region and/or limited parameter region for the Bohr frequencies of the subsystems. In this paper, we present a formalism that leads to the time-convolutionless (time-local) master equation obtained by extending the global approach beyond the Born-Markov and secular approximations. We apply it to the excitation energy transfer between interacting sites in which only the terminal site weakly interacts with a bosonic environment of finite temperature in a manner beyond the rotating-wave approximation. We find that the formulation (1) gives the short-time behavior while preserving positivity, (2) shows the oscillatory features that the secular approximation would obscure, and (3) leads to a stationary state very near to the Gibbs state for the total Hamiltonian of the relevant system.
It is known that the origin of the deviations from standard thermodynamics proceed from the strong coupling to the bath. Here, it is shown that these deviations are related to the power spectrum of the bath. Specifically, it is shown that the system thermal-equilibrium-state cannot be characterized by the canonical Boltzmann's distribution in quantum mechanics. This is because the uncertainty principle imposed a lower bound of the dispersion of the total energy of the system that is dominated by the spectral density of the bath. However, in the classical case, for a wide class of systems that interact via central forces with pairwise-self-interacting environment, the system thermal equilibrium state is exactly characterized by the canonical Boltzmann distribution. As a consequence of this analysis and taking into account all energy scales in the system and reservoir interaction, an effective coupling to the environment is introduced. Sample computations in different regimes predicted by this effective coupling are shown. Specifically, in the strong coupling effective regime, the system exhibits deviations from standard thermodynamics and in the weak coupling effective regime, quantum features such as stationary entanglement are possible at high temperatures. Moreover, it is known that the spectrum of thermal baths depends on the non-Markovian character. Hence, non-Markovian interactions have a important role in the thermal equilibrium state of physical systems. For example, in quantum optomechanics is looked up to cool the mechanical system through an auxiliary system which generally is a cavity. This cooling process takes into account the non-Markovian interaction and as it is shown here, it is more effective than if we use only the Markovian approximation in the equation of motion for the different modes.