We investigate the efficiency of a quantum Carnot engine based on open quantum dynamics theory. The model includes time-dependent external fields for the subsystems controlling the isothermal and isentropic processes and for the system-bath (SB) interactions controlling the transition between these processes. Numerical simulations are conducted in a nonperturbative and non-Markovian SB coupling regime by using the hierarchical equations of motion under these fields at different cycle frequencies. The work applied to the total system and the heat exchanged with the baths are rigorously evaluated. In addition, by regarding quasi-static work as free energy, we compute the quantum thermodynamic variables and analyze the simulation results by using thermodynamic work diagrams for the first time. Analysis of these diagrams indicates that, in the strong SB coupling region, the fields for the SB interactions are major sources of work, while in other regions, the field for the subsystem is a source of work. We find that the maximum efficiency is achieved in the quasi-static case and is determined solely by the bath temperatures, regardless of the SB coupling strength, which is a numerical manifestation of Carnot's theorem.
We investigate the efficiency of a quantum Carnot engine based on open quantum dynamics theory. The model includes time-dependent external fields for the subsystems controlling the isothermal and isentropic processes and for the system-bath (SB) interactions controlling the transition between these processes. Numerical simulations are conducted in a nonperturbative and non-Markovian SB coupling regime by using the hierarchical equations of motion under these fields at different cycle frequencies. The work applied to the total system and the heat exchanged with the baths are rigorously evaluated. In addition, by regarding quasi-static work as free energy, we compute the quantum thermodynamic variables and analyze the simulation results by using thermodynamic work diagrams for the first time. Analysis of these diagrams indicates that, in the strong SB coupling region, the fields for the SB interactions are major sources of work, while in other regions, the field for the subsystem is a source of work. We find that the maximum efficiency is achieved in the quasi-static case and is determined solely by the bath temperatures, regardless of the SB coupling strength, which is a numerical manifestation of Carnot's theorem.
We developed a computer code for the thermodynamic quantum Fokker-Planck equations (T-QFPE), derived from a thermodynamic system-bath model. This model consists of an anharmonic subsystem coupled to multiple Ohmic baths at different temperatures, which are connected to or disconnected from the subsystem as a function of time. The code numerically integrates the T-QFPE and their classical expression to simulate isothermal, isentropic, thermostatic, and entropic processes in both quantum and classical cases. The accuracy of the results was verified by comparing the analytical solutions of the Brownian oscillator. In addition, we illustrated a breakdown of the Markovian Lindblad-master equation in the pure quantum regime. As a demonstration, we simulated a thermostatic Stirling engine employed to develop non-equilibrium thermodynamics [S. Koyanagi and Y. Tanimura, J. Chem. Phys. 161, 114113 (2024)] under quasi-static conditions. The quasi-static thermodynamic potentials, described as intensive and extensive variables, were depicted as work diagrams. In the classical case, the work done by the external field is independent of the system-bath coupling strength. In contrast, in the quantum case, the work decreases as the coupling strength increases due to quantum entanglement between the subsystem and bath. The codes were developed for multicore processors using Open Multi-Processing (OpenMP) and for graphics processing units using the Compute Unified Device Architecture. These codes are provided in the supplementary material.
We developed a computer code for the thermodynamic quantum Fokker-Planck equations (T-QFPE), derived from a thermodynamic system-bath model. This model consists of an anharmonic subsystem coupled to multiple Ohmic baths at different temperatures, which are connected to or disconnected from the subsystem as a function of time. The code numerically integrates the T-QFPE and their classical expression to simulate isothermal, isentropic, thermostatic, and entropic processes in both quantum and classical cases. The accuracy of the results was verified by comparing the analytical solutions of the Brownian oscillator. Additionally, we illustrated a breakdown of the Markovian Lindblad-master equation in the pure quantum regime. As a demonstration, we simulated a thermostatic Stirling engine employed to develop non-equilibrium thermodynamics [S. Koyanagi and Y. Tanimura, J. Chem. Phys 161, 114113 (2024)] under quasi-static conditions. The quasi-static thermodynamic potentials, described as intensive and extensive variables, were depicted as work diagrams. In the classical case, the work done by the external field is independent of the system-bath coupling strength. In contrast, in the quantum case, the work decreases as the coupling strength increases due to quantum entanglement between the subsystem and bath. The codes were developed for multicore processors using Open multiprocessing (OpenMP) and for graphics processing units (GPU) using the Compute United Device Architecture (CUDA). These codes are provided as supplementary materials.
By using the quasi-equilibrium Helmholtz energy, which is defined as the thermodynamic work in a quasi-static process, we investigate the thermal properties of both an isothermal process and a transition process between the adiabatic and isothermal states (adiabatic transition). Here, the work is defined by the change in energy from a steady state to another state under a time-dependent perturbation. In particular, the work for a quasi-static change is regarded as thermodynamic work. We employ a system-bath model that involves time-dependent perturbations in both the system and the system-bath interaction. We conduct numerical experiments for a three-stroke heat machine (a Kelvin-Planck cycle). For this purpose, we employ the hierarchical equations of motion (HEOM) approach. These experiments involve an adiabatic transition field that describes the operation of an adiabatic wall between the system and the bath. Thermodynamic-work diagrams for external fields and their conjugate variables, similar to the P-V diagram, are introduced to analyze the work done for the system in the cycle. We find that the thermodynamic efficiency of this machine is zero because the field for the isothermal processes acts as a refrigerator, whereas that for the adiabatic wall acts as a heat engine. This is a numerical manifestation of the Kelvin-Planck statement, which states that it is impossible to derive the mechanical effects from a single heat source. These HEOM simulations serve as a rigorous test of thermodynamic formulations because the second law of thermodynamics is only valid when the work involved in the operation of the adiabatic wall is treated accurately.
Abstract We study the thermodynamic performance of a finite-time non-regenerative quantum Stirling-like cycle used as a heat engine. We consider specifically the case in which the working substance (WS) is a two-level system (TLS). The Stirling cycle is made of two isochoric transformations separated by a compression and an expansion stroke during which the WS is in contact with a thermal reservoir. To describe these two strokes we derive a non-Markovian master equation which allows to study the real-time dynamics of a driven open quantum system with arbitrary fast driving. Following the real-time dynamics of the WS using this master equation, the endpoints of the isotherms can deviate from the equilibrium thermal states. The role of this deviation in the performance of the heat engine is addressed. We found that the finite-time dynamics and thermodynamics of the cycle depend non-trivially on the different time scales at play. In particular, driving the WS at a time scale comparable to the resonance time of the bath enhances the performance of the cycle and allows for an efficiency higher than the efficiency of the quasistatic cycle, but still below the Carnot bound. However, by adding thermalization of the WS with the baths at the end of compression/expansion processes one recovers the conventional scenario in which efficiency decreases by speeding up the processes. In addition, the performance of the cycle is dependent on the compression/expansion speeds asymmetrically, which suggests new freedom in optimizing quantum heat engines. The maximum output power and the maximum efficiency are obtained almost simultaneously when the real-time endpoints of the compression/expansion processes are considered instead of the equilibrium thermal endpoint states. However, the net extractable work always declines by speeding up the drive.
We present a scheme to evaluate thermodynamic variables for a system coupled to a heat bath under a time-dependent external force using the quasi-static Helmholtz energy from the numerically "exact" hierarchical equations of motion (HEOM). We computed the entropy produced by a spin system strongly coupled to a non-Markovian heat bath for various temperatures. We showed that when changes to the external perturbation occurred sufficiently slowly, the system always reached thermal equilibrium. Thus, we calculated the Boltzmann entropy and the von Neumann entropy for an isothermal process, as well as various thermodynamic variables, such as changes in internal energies, heat, and work, for a system in quasi-static equilibrium based on the HEOM. We found that although the characteristic features of the system entropies in the Boltzmann and von Neumann cases as a function of the system-bath coupling strength are similar, those for the total entropy production are completely different. The total entropy production in the Boltzmann case is always positive, whereas that in the von Neumann case becomes negative if we chose a thermal equilibrium state of the total system (an unfactorized thermal equilibrium state) as the initial state. This is because the total entropy production in the von Neumann case does not properly take into account the contribution of the entropy from the system-bath interaction. Thus, the Boltzmann entropy must be used to investigate entropy production in the fully quantum regime. Finally, we examined the applicability of the Jarzynski equality.
A nonstochastic quantum engine is one that operates in a cycle of transformations in which no sources of stochasticity, such as thermal baths and projective measurements, are present and, therefore, no entropy is generated in the driven system. Defining work and heat as the energy corresponding to different types of transformations between pure states, we arrive at an expression similar to the first law of thermodynamics and prove a version of the Kelvin-Planck statement for the second law of thermodynamics. Essentially, the first law can be obtained thanks to the normalization condition of a quantum state and the second law can be obtained thanks to the orthogonalization condition between energy eigenstates. For nonstochastic engines that operate between two given energy gaps, we prove a version of Carnot's theorem. Regarding operationalization, we present a protocol that leads the system through a cycle in which heat exchange occurs by performing two quantum quenches separated by a precise time interval and involving an energy-level anticrossing. Furthermore, with this protocol it is possible to make the engine's efficiency as close to 1 as one wants; however, efficiency equal to 1 is a case prohibited by the version of the Kelvin-Planck statement that we proved. Finally, we illustrate these results in an exactly solvable single-qubit model.