The dynamical convergence of a system to the thermal distribution, or Gibbs state, is a standard assumption across all of the physical sciences. The Gibbs state is determined just by temperature and energies of the system. However, at decreasing system sizes, i.e., for nanoscale and quantum systems, the interaction with their environments is not negligible. The question then arises: Is the system's steady state still the Gibbs state? If not, how may the steady state depend on the interaction details? Here, we provide an overview of recent progress on answering these questions. We expand on the state of the art along two general avenues: First, we take the static point-of-view, which postulates the so-called mean force Gibbs state. This view is commonly adopted in the field of strong coupling thermodynamics, where modified laws of thermodynamics and nonequilibrium fluctuation relations are established on the basis of this modified state. Second, we take the dynamical point of view, originating from the field of open quantum systems, which examines the time-asymptotic steady state within two paradigms. We describe the mathematical paradigm, which proves return to equilibrium, i.e., convergence to the mean force Gibbs state, and then discuss a number of microscopic physical methods, particularly master equations. We conclude with a summary of established links between statics and equilibration dynamics and provide an extensive list of open problems. This comprehensive overview will be of interest to researchers in the wider fields of quantum thermodynamics, open quantum systems, mesoscopic physics, statistical physics, and quantum optics and will find applications whenever energy is exchanged on the nanoscale, from quantum chemistry and biology to magnetism and nanoscale heat management.
The dynamical convergence of a system to the thermal distribution, or Gibbs state, is a standard assumption across all of the physical sciences. The Gibbs state is determined just by temperature and energies of the system. However, at decreasing system sizes, i.e., for nanoscale and quantum systems, the interaction with their environments is not negligible. The question then arises: Is the system's steady state still the Gibbs state? If not, how may the steady state depend on the interaction details? Here, we provide an overview of recent progress on answering these questions. We expand on the state of the art along two general avenues: First, we take the static point-of-view, which postulates the so-called mean force Gibbs state. This view is commonly adopted in the field of strong coupling thermodynamics, where modified laws of thermodynamics and nonequilibrium fluctuation relations are established on the basis of this modified state. Second, we take the dynamical point of view, originating from the field of open quantum systems, which examines the time-asymptotic steady state within two paradigms. We describe the mathematical paradigm, which proves return to equilibrium, i.e., convergence to the mean force Gibbs state, and then discuss a number of microscopic physical methods, particularly master equations. We conclude with a summary of established links between statics and equilibration dynamics and provide an extensive list of open problems. This comprehensive overview will be of interest to researchers in the wider fields of quantum thermodynamics, open quantum systems, mesoscopic physics, statistical physics, and quantum optics and will find applications whenever energy is exchanged on the nanoscale, from quantum chemistry and biology to magnetism and nanoscale heat management.
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.
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.
In a series of papers, we intend to take the perspective of open quantum systems and examine from their nonequilibrium dynamics the conditions when the physical quantities, their relations, and the laws of thermodynamics become well defined and viable for quantum many-body systems. We first describe how an open-system nonequilibrium dynamics (ONEq) approach is different from the closed combined system + environment in a global thermal state (CGTs) setup. Only after the open system equilibrates will it be amenable to conventional thermodynamics descriptions, thus quantum thermodynamics (QTD) comes at the end rather than assumed in the beginning. The linkage between the two comes from the reduced density matrix of ONEq in that stage having the same form as that of the system in the CGTs. We see the open-system approach having the advantage of dealing with nonequilibrium processes as many experiments in the near future will call for. Because it spells out the conditions of QTD's existence, it can also aid us in addressing the basic issues in quantum thermodynamics from first principles in a systematic way. We then study one broad class of open quantum systems where the full nonequilibrium dynamics can be solved exactly, that of the quantum Brownian motion of N strongly coupled harmonic oscillators, interacting strongly with a scalar-field environment. In this paper, we focus on the internal energy, heat capacity, and the third law. We show for this class of physical models, amongst other findings, the extensive property of the internal energy, the positivity of the heat capacity, and the validity of the third law from the perspective of the behavior of the heat capacity toward zero temperature. These conclusions obtained from exact solutions and quantitative analysis clearly disprove claims of negative specific heat in such systems and dispel allegations that in such systems the validity of the third law of thermodynamics relies on quantum entanglement. They are conceptually and factually unrelated issues. Entropy and entanglement will be the main theme of our second paper on this subject matter.
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.
The thermodynamical behavior of quantum systems at the nanoscale is often very difficult to capture via standard frameworks of thermodynamics. The latter is, in fact, an equilibrium theory whose predictions are typically only valid on average, and in regimes where systems are composed of a very large number of constituents. In reality, the thermodynamical behavior of nanoscale systems can be much more constrained that what is predicted by macroscopic thermodynamics, due to the unavoidable impact of fluctuations. As a result, the fundamental limitations to a system's dynamics induced by macroscopic thermodynamics might turn out to be considerably less stringent than what can actually be observed at those scales. The theory of open quantum systems is certainly a powerful tool in this context, and can provide solutions which go beyond equilibrium treatments, but solving the dynamics of an open system requires detailed information about its microscopic structure (e.g. system-environment interactions and coupling strengths). In other words, one of the great advantages of macroscopic thermodynamics, i.e. its universality and independence of microscopic details, might be essentially lost if we can only infer thermodynamical results once we specify the full microscopic structure of our system-environment interaction. This highlights the necessity for a framework of thermodynamics that is well suited for studying the behavior of small quantum systems far from equilibrium, but can still be applied to physical systems in a universal way, i.e., without having to specify full microscopic information. Quantum Resource Theories (QRTs), and in particular the formulations of quantum thermodynamics that have emerged from them, constitute a promising tool in this direction. However, these models of thermodynamics have not yet been extensively applied to realistic physical platform, and their consequences on known thermodynamical processes are still unexplored. Furthermore, going beyond a purely thermodynamical context, a case can be made for the use of general QRTs as benchmarking tools for the certification of certain quantum resources. In other words, QRTs could be used to find fundamental bounds to physical quantities or impossibility results (in the form of no-go theorems) that, when compared to experimental data, can be used to falsify specific hypotheses. In this thesis, both these directions will be explored, by considering resource-theoretical questions that are relevant for different physical platforms. These will include the photochemical process of photoisomerization, heat transport in harmonic systems, and tabletop tests of quantum gravity.