The equilibrium state of a quantum system can deviate from the Gibbs state if the system-environment (SE) coupling is not weak. An analytical expression for this mean force Gibbs state (MFGS) is known in the ultrastrong coupling (USC) regime for the Caldeira-Leggett (CL) model that assumes a harmonic environment. Here, we derive analytical expressions for the MFGS in the USC regime for more general SE models. For all the generalized models considered here, we find the USC state to be diagonal in the basis set by the SE interaction, just like in the CL case. While for the generic model considered, the corresponding USC-MFGS is found to alter from the CL result, we do identify a class of models more general than the CL model for which the CL-USC result remains unchanged. We also provide numerical verification for our results. These results provide key tools for the study of strong coupling quantum thermodynamics and several quantum chemistry and biology problems under more realistic SE models, going beyond the CL model.
The equilibrium state of a quantum system can deviate from the Gibbs state if the system-environment (SE) coupling is not weak. An analytical expression for this mean force Gibbs state (MFGS) is known in the ultrastrong coupling (USC) regime for the Caldeira-Leggett (CL) model that assumes a harmonic environment. Here, we derive analytical expressions for the MFGS in the USC regime for more general SE models. For all the generalized models considered here, we find the USC state to be diagonal in the basis set by the SE interaction, just like in the CL case. While for the generic model considered, the corresponding USC-MFGS is found to alter from the CL result, we do identify a class of models more general than the CL model for which the CL-USC result remains unchanged. We also provide numerical verification for our results. These results provide key tools for the study of strong coupling quantum thermodynamics and several quantum chemistry and biology problems under more realistic SE models, going beyond the CL model.
The Gibbs state is widely taken to be the equilibrium state of a system in contact with an environment at temperature T. However, non-negligible interactions between system and environment can give rise to an altered state. Here we derive general expressions for this mean force Gibbs state, valid for any system that interacts with a bosonic reservoir. First, we derive the state in the weak coupling limit and find that, in general, it maintains coherences with respect to the bare system Hamiltonian. Second, we develop a new expansion method suited to investigate the ultrastrong coupling regime. This allows us to derive the explicit form for the mean force Gibbs state, and we find that it becomes diagonal in the basis set by the system-reservoir interaction instead of the system Hamiltonian. Several examples are discussed including a single qubit, a three-level V-system and two coupled qubits all interacting with bosonic reservoirs. The results shed light on the presence of coherences in the strong coupling regime, and provide key tools for nanoscale thermodynamics investigations.
The Gibbs state is widely taken to be the equilibrium state of a system in contact with an environment at temperature T. However, non-negligible interactions between system and environment can give rise to an altered state. Here, we derive general expressions for this mean force Gibbs state, valid for any system that interacts with a bosonic reservoir. First, we derive the state in the weak coupling limit and find that, in general, it maintains coherences with respect to the bare system Hamiltonian. Second, we develop a new expansion method suited to investigate the ultrastrong coupling regime. This allows us to derive the explicit form for the mean force Gibbs state, and we find that it becomes diagonal in the basis set by the system-reservoir interaction instead of the system Hamiltonian. Several examples are discussed including a single qubit, a three-level V-system, and two coupled qubits all interacting with bosonic reservoirs. The results shed light on the presence of coherences in the strong coupling regime, and provide key tools for nanoscale thermodynamics investigations.
An open quantum system interacting with a heat bath at a given temperature is expected to reach the mean force Gibbs (MFG) state as a steady state. The MFG state is given by tracing out the bath degrees of freedom from the equilibrium Gibbs state of the total system plus bath. When the interaction between the system and the bath is not negligible, it is different from the usual system Gibbs state obtained from the system Hamiltonian only. Using the path integral method, we present the exact MFG state for a coupled system of quantum harmonic oscillators in contact with multiple thermal baths at the same temperature. We develop a nonperturbative method to calculate the covariances with respect to the MFG state. By comparing them with those obtained from the system Gibbs state, we find that the effect of coupling to the bath decays exponentially as a function of the distance from the system-bath boundary. This is similar to the skin effect found recently for a quantum spin chain interacting with an environment. Using the exact results, we also investigate the ultrastrong coupling limit where the coupling between the system and the bath gets arbitrarily large and makes a connection with the recent result found for a general quantum system.
When the strength of interaction between a quantum system and bath is non-negligible, the equilibrium state can deviate from the Gibbs state. But the expression of such a mean force Gibbs state in an arbitrary parameter regime is unknown and is numerically challenging to determine. In this work, we first review the local harmonic approximation to this problem [Maier et al., Phys. Rev. E 81, 021107 (2010)], which can accurately determine the mean force Gibbs state when either the system-bath coupling or the temperature is large, or when the third and higher derivatives of the potential are small compared to certain system-bath specific parameters. In the appropriate limit, we show that the local harmonic approximation reduces to the ultra-strong coupling and high temperature results recently derived in the literature. After deriving an estimate for the error induced by this method, we apply it to study some systems, like a quartic oscillator and a particle in a quartic double-well potential. We also apply this method to analyze the proton tunneling problem in a DNA recently studied in literature [Slocombe et al., Comm. Phys., vol. 5, no. 1, p. 109, 2022], where our results suggest the equilibrium value of the probability of mutation to be orders of magnitude lower than the steady state value obtained there (10−8 vs 10−4).
In the framework of the theory of open quantum systems, we derive quantum master equations for the ultrastrong system-bath coupling regime and, more generally, the strong-decoherence regime. In this regime, the strong decoherence is complemented by slow relaxation processes. We use a generalization of the F\"orster and modified Redfield perturbation theories known in the theory of excitation-energy transfer. Also, we show that the mean-force Gibbs state in the corresponding limits is stationary for the derived master equations.
When the coupling of a quantum system to its environment is nonnegligible, its steady state is known to deviate from the textbook Gibbs state. The Bloch-Redfield quantum master equation, one of the most widely adopted equations for solving the open quantum dynamics, cannot predict all the deviations of the steady state of a quantum system from the Gibbs state. In this paper, for a generic spin-boson model, we use a higher-order quantum master equation (in system-environment coupling strength) to analytically calculate all the deviations of the steady state of the quantum system up to second order in coupling strength. We also show that this steady state is exactly identical to the corresponding generalized Gibbs state, the so-called quantum mean force Gibbs state, at arbitrary temperature. All these calculations are highly general, making them immediately applicable to a wide class of systems well modeled by the spin-Boson model, spanning a diverse range of topics, from nanomaterials to various condensed-phase processes, and quantum computing (e.g., environment-induced corrections to the steady state of a superconducting qubit). As an example, we use our results to study the dynamics and the steady state of a solid-state double-quantum-dot system under physically relevant choices of parameters.