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The Journal of Chemical Physics

The quantum heat engine and heat pump: An irreversible thermodynamic analysis of the three-level amplifier

Eitan Geva, Ronnie Kosloff

Published May 15, 1996• 178 citations
Publisher

Abstract

The manifestations of the three laws of thermodynamics are explored in a model of an irreversible quantum heat engine. The engine is composed of a three-level system simultaneously coupled to hot and cold heat baths, and driven by an oscillating external field. General quantum heat baths are considered, which are weakly coupled to the three-level system. The work reservoir is modeled by a classical electro-magnetic field of arbitrary intensity, which is driving the three-level system. The first law of thermodynamics is related to the rate of change of energy obtained from the quantum master equation in the Heisenberg picture. The fluxes of the thermodynamic heat and work are then directly related to the expectation values of quantum observables. An analysis of the standard quantum master equation for the amplifier, first introduced by Lamb, is shown to be thermodynamically inconsistent when strong driving fields are used. A generalized master equation is rigorously derived, starting from the underlying quantum dynamics, which includes relaxation terms that explicitly depend upon the field. For weak fields the generalized master equation reduces to the standard equation. In very intense fields the amplifier splits into two heat engines. One engine accelerates as the field intensifies, while the other slows down and eventually switches direction to become a heat pump. The relative weight of the slower engine increases with the field intensity, leading to a maximum in power as a function of the field intensity. The amplifier is shown to go through four ‘‘phases’’ as the driving field is intensified, throughout all of which the second law of thermodynamics is generally satisfied. One phase corresponds to a ‘‘refrigeration window’’ which allows for the extraction of heat out of a cold bath of temperatures down to the absolute zero. This window disappears at absolute zero, which is conjectured to be a dynamical manifestation of the third law of thermodynamics.

DOI
10.1063/1.471453

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The manifestations of the three laws of thermodynamics are explored in a model of an irreversible quantum heat engine. The engine is composed of a three-level system simultaneously coupled to hot and cold heat baths, and driven by an oscillating external field. General quantum heat baths are considered, which are weakly coupled to the three-level system. The work reservoir is modeled by a classical electro-magnetic field of arbitrary intensity, which is driving the three-level system. The first law of thermodynamics is related to the rate of change of energy obtained from the quantum master equation in the Heisenberg picture. The fluxes of the thermodynamic heat and work are then directly related to the expectation values of quantum observables. An analysis of the standard quantum master equation for the amplifier, first introduced by Lamb, is shown to be thermodynamically inconsistent when strong driving fields are used. A generalized master equation is rigorously derived, starting from the underlying quantum dynamics, which includes relaxation terms that explicitly depend upon the field. For weak fields the generalized master equation reduces to the standard equation. In very intense fields the amplifier splits into two heat engines. One engine accelerates as the field intensifies, while the other slows down and eventually switches direction to become a heat pump. The relative weight of the slower engine increases with the field intensity, leading to a maximum in power as a function of the field intensity. The amplifier is shown to go through four ‘‘phases’’ as the driving field is intensified, throughout all of which the second law of thermodynamics is generally satisfied. One phase corresponds to a ‘‘refrigeration window’’ which allows for the extraction of heat out of a cold bath of temperatures down to the absolute zero. This window disappears at absolute zero, which is conjectured to be a dynamical manifestation of the third law of thermodynamics.
The finite-rate performance of a quantum heat engine, constructed from a three-level amplifier, is analyzed. Consistent definitions of thermodynamical quantities in terms of quantum observables are postulated. The performance is analyzed in steady state, where the operation of the amplifier only influences the surroundings. Quantum master equations describe the irreversible dynamics induced by the coupling of the working medium to the reservoirs. It is shown that the standard assumption of field-independent dissipation is inconcistent with thermodynamics. Field-dependent relaxation equations, based upon the semigroup approach, and consistent with thermodynamics, are formulated. These equations are valid if the time scale of the external field is slow compared to that associated with the bath fluctuations. The steady-state values of the thermodynamical quantities are evaluated. The power is found to have maxima as a function of important controls, such as the field amplitude, frequency, and the coupling with the baths. The existence and locations of these maxima differ from those obtained in the standard treatment, where the dissipation is field independent. The irreversible nature of engine operation is due to the finite rate of heat transfer and a genuine ``quantum-friction'' loss term due to dephasing.
Quantum thermodynamics supplies a consistent description of quantum heat engines and refrigerators up to a single few-level system coupled to the environment. Once the environment is split into three (a hot, cold, and work reservoir), a heat engine can operate. The device converts the positive gain into power, with the gain obtained from population inversion between the components of the device. Reversing the operation transforms the device into a quantum refrigerator. The quantum tricycle, a device connected by three external leads to three heat reservoirs, is used as a template for engines and refrigerators. The equation of motion for the heat currents and power can be derived from first principles. Only a global description of the coupling of the device to the reservoirs is consistent with the first and second laws of thermodynamics. Optimization of the devices leads to a balanced set of parameters in which the couplings to the three reservoirs are of the same order and the external driving field is in resonance. When analyzing refrigerators, one needs to devote special attention to a dynamical version of the third law of thermodynamics. Bounds on the rate of cooling when Tc→0 are obtained by optimizing the cooling current. All refrigerators as Tc→0 show universal behavior. The dynamical version of the third law imposes restrictions on the scaling as Tc→0 of the relaxation rate γc and heat capacity cV of the cold bath.
We present a detailed thermodynamic analysis of a three-level quantum heat engine coupled continuously to hot and cold reservoirs. The system is driven by an oscillating external field and is described by the Markovian quantum master equation. We use the general form of the dissipator which is consistent with thermodynamics. We calculate the heat, power, and efficiency of the system for the heat-engine operating regime and also examine the thermodynamic uncertainty relation. The efficiency of the system is strongly dependent on the structure of the dissipator, and the correlations between different levels can be an obstacle for ideal operation. In quantum systems, the heat flux is decomposed into the population and coherent parts. The coherent part is specific to quantum systems, and in contrast to the population part, it cannot be expressed by a simple series expansion in the linear-response regime. We discuss how the interplay between the population and coherent parts affects the performance of the heat engine.
The fundamentals of a quantum heat engine are derived from first principles. The study is based on the equation of motion of a minimum set of operators, which is then used to define the state of the system. The relation between the quantum framework and the thermodynamical observables is examined. A four-stroke heat engine model with a coupled two-level system as a working fluid is used to explore the fundamental relations. In the model used, the internal Hamiltonian does not commute with the external control field, which defines the two adiabatic branches. Heat is transferred to the working fluid by coupling to hot and cold reservoirs under constant field values. Explicit quantum equations of motion for the relevant observables are derived on all branches. The dynamics on the heat transfer constant field branches is solved in closed form. On the adiabats, a general numerical solution is used and compared with a particular analytic solution. These solutions are combined to construct the cycle of operation. The engine is then analyzed in terms of the frequency-entropy and entropy-temperature graphs. The irreversible nature of the engine is the result of finite heat transfer rates and frictionlike behavior due to noncommutability of the internal and external Hamiltonians.
The rate of temperature decrease of a cooled quantum bath is studied as its temperature is reduced to absolute zero. The third law of thermodynamics is then quantified dynamically by evaluating the characteristic exponent ζ of the cooling process dT(t)/dt∼-T^{ζ} when approaching absolute zero, T→0. A continuous model of a quantum refrigerator is employed consisting of a working medium composed either by two coupled harmonic oscillators or two coupled two-level systems. The refrigerator is a nonlinear device merging three currents from three heat baths: a cold bath to be cooled, a hot bath as an entropy sink, and a driving bath which is the source of cooling power. A heat-driven refrigerator (absorption refrigerator) is compared to a power-driven refrigerator. When optimized, both cases lead to the same exponent ζ, showing a lack of dependence on the form of the working medium and the characteristics of the drivers. The characteristic exponent is therefore determined by the properties of the cold reservoir and its interaction with the system. Two generic heat bath models are considered: a bath composed of harmonic oscillators and a bath composed of ideal Bose/Fermi gas. The restrictions on the interaction Hamiltonian imposed by the third law are discussed. In the Appendices, the theory of periodically driven open systems and its implication for thermodynamics are outlined.