We formulate a thermodynamic theory applicable to both classical and quantum systems. These systems are depicted as thermodynamic system-bath models capable of handling isothermal, isentropic, thermostatic, and entropic processes. Our approach is based on the use of a dimensionless thermodynamic potential expressed as a function of the intensive and extensive thermodynamic variables. Using the principles of dimensionless minimum work and dimensionless maximum entropy derived from quasi-static changes of external perturbations and temperature, we obtain the Massieu-Planck potentials as entropic potentials and the Helmholtz-Gibbs potentials as free energy. These potentials can be interconverted through time-dependent Legendre transformations. Our results are verified numerically for an anharmonic Brownian system described in phase space using the low-temperature quantum Fokker-Planck equations in the quantum case and the Kramers equation in the classical case, both developed for the thermodynamic system-bath model. Thus, we clarify the conditions for thermodynamics to be valid even for small systems described by Hamiltonians and establish a basis for extending thermodynamics to non-equilibrium conditions.
We formulate a thermodynamic theory applicable to both classical and quantum systems. These systems are depicted as thermodynamic system-bath models capable of handling isothermal, isentropic, thermostatic, and entropic processes. Our approach is based on the use of a dimensionless thermodynamic potential expressed as a function of the intensive and extensive thermodynamic variables. Using the principles of dimensionless minimum work and dimensionless maximum entropy derived from quasi-static changes of external perturbations and temperature, we obtain the Massieu-Planck potentials as entropic potentials and the Helmholtz-Gibbs potentials as free energy. These potentials can be interconverted through time-dependent Legendre transformations. Our results are verified numerically for an anharmonic Brownian system described in phase space using the low-temperature quantum Fokker-Planck equations in the quantum case and the Kramers equation in the classical case, both developed for the thermodynamic system-bath model. Thus, we clarify the conditions for thermodynamics to be valid even for small systems described by Hamiltonians and establish a basis for extending thermodynamics to non-equilibrium conditions.
Abstract Quantum thermodynamics describes dynamic processes by means of the operators of entropy production P and time t . P and t do not commute. It exists the non-vanishing t–P commutator [ t , P ]=ik. Here the Boltzmann constant k has the physical meaning of a quantum of entropy. The t–P commutator immediately leads us to the t–P uncertainty relation ΔtΔP≥k/2. Hence the observables t and P are not sharply defined simultaneously. Similar uncertainty relations can also be expected for other pairs of conjugate variables with products of the physical meaning of an entropy. The free energy F and the reciprocal temperature (1/T) are the respective conjugate variables of an isolated system of many particles, which leads us to the F–(1/T) uncertainty relation ǀΔFǁΔ(1/T)ǀ≥k/2. It can be traced back to the t–P uncertainty relation mentioned above. In this way the Helmholtz free energy F and the temperatur T are introduced into quantum thermodynamics. The uncertainties ǀΔFǀ→0 and ǀΔTǀ→0 are negligible at low temperatures T→0, and quantum thermodynamics turns into the time-independent classical thermodynamics. Against this the uncertainties ǀΔFǀ→∞ and ǀΔTǀ→∞ grow unlimited at high temperatures T→∞, and classical thermodynamics loses its sense. In the limit of one particle the uncertainties cannot be neglected even at low temperatures. However a detailed discussion shows that the free energy f of a single particle vanishes within the whole range of temperatures T. This defines the particle entropy σ=ε/T=ak. The dimensionless entropy number a connects the particle energy ε=akT with the temperature T. The entropy number a of a single (s) independent particle can be calculated with the extended, temperature-dependent Schrödinger equation A s φ=aφ. Here A s=−(Λ 2/4π)∇2 means the dimensionless entropy operator describing the entropy number a and thus the particle entropy σ=ak. Λ is the thermal de Broglie wave length. Finally we calculate by means of quantized particle entropies σ the internal energy E, the Helmholtz free energy F, the entropy S, the chemical potential μ, and the equation of state of an ideal gas of N monatomic free particles in full agreement with classical thermodynamics. We also calculate the partition function q=V/Λ 3 of a single free particle within the volume V. Here Λ 3 is a small volume element taking into account the wave–particle dualism of a single free particle of mass m at temperature T. Extension to a system of N free particles leads us to a simple geometrical model and to the conclusion that an ideal gas of independent particles becomes instable below a critical temperature T C. T C corresponds to the critical temperature T BE of Bose–Einstein condensation.
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.
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.
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.
Thermodynamics and information have intricate interrelations. Often thermodynamics is considered to be the logical premise to justify that information is physical - through Landauer's principle -, thereby also linking information and thermodynamics. This approach towards information has been instrumental to understand thermodynamics of logical and physical processes, both in the classical and quantum domain. In the present work, we formulate thermodynamics as an exclusive consequence of information conservation. The framework can be applied to the most general situations, beyond the traditional assumptions in thermodynamics: we allow systems and thermal baths to be quantum, of arbitrary sizes and even possessing inter-system correlations.Here, systems and baths are not treated differently, rather both are considered on an equal footing. This leads us to introduce a ''temperature''-independent formulation of thermodynamics. We rely on the fact that, for a fixed amount of information, measured by the von Neumann entropy, any system can be transformed to a state with the same entropy that possesses minimal energy. This state, known as a completely passive state, acquires Boltzmann-Gibbs canonical form with an intrinsic temperature . We introduce the notions of bound and free energy and use them to quantify heat and work, respectively. Guided by the principle of information conservation, we develop universal notions of equilibrium, heat and work, Landauer's principle and universal fundamental laws of thermodynamics. We demonstrate that the maximum efficiency of a quantum engine with a finite bath is in general lower than that of an ideal Carnot engine. We introduce a resource theoretic framework for our intrinsic temperature based thermodynamics, within which we address the problem of work extraction and state transformations. Finally, the framework is extended to multiple conserved quantities.
Thermodynamics and information have intricate interrelations. Often thermodynamics is considered to be the logical premise to justify that information is physical - through Landauer's principle -, thereby also linking information and thermodynamics. This approach towards information has been instrumental to understand thermodynamics of logical and physical processes, both in the classical and quantum domain. In the present work, we formulate thermodynamics as an exclusive consequence of information conservation. The framework can be applied to the most general situations, beyond the traditional assumptions in thermodynamics: we allow systems and thermal baths to be quantum, of arbitrary sizes and even possessing inter-system correlations.Here, systems and baths are not treated differently, rather both are considered on an equal footing. This leads us to introduce a ''temperature''-independent formulation of thermodynamics. We rely on the fact that, for a fixed amount of information, measured by the von Neumann entropy, any system can be transformed to a state with the same entropy that possesses minimal energy. This state, known as a completely passive state, acquires Boltzmann-Gibbs canonical form with an intrinsic temperature. We introduce the notions of bound and free energy and use them to quantify heat and work, respectively. Guided by the principle of information conservation, we develop universal notions of equilibrium, heat and work, Landauer's principle and universal fundamental laws of thermodynamics. We demonstrate that the maximum efficiency of a quantum engine with a finite bath is in general lower than that of an ideal Carnot engine. We introduce a resource theoretic framework for our intrinsic temperature based thermodynamics, within which we address the problem of work extraction and state transformations. Finally, the framework is extended to multiple conserved quantities.