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arXiv:quant-ph/0601056

Quantum Brownian motion and the Third Law of thermodynamics

Peter Hänggi A, Gert‐Ludwig Ingold

Published Jan 10, 2006• 21 citations
arXivHTMLPDF

Abstract

The quantum thermodynamic behavior of small systems is investigated in presence of finite quantum dissipation. We consider the archetype cases of a damped harmonic oscillator and a free quantum Brownian particle. A main finding is that quantum dissipation helps to ensure the validity of the Third Law. For the quantum oscillator, finite damping replaces the zero-coupling result of an exponential suppression of the specific heat at low temperatures by a power-law behavior. Rather intriguing is the behavior of the free quantum Brownian particle. In this case, quantum dissipation is able to restore the Third Law: Instead of being constant down to zero temperature, the specific heat now vanishes proportional to temperature with an amplitude that is inversely proportional to the ohmic dissipation strength. A distinct subtlety of finite quantum dissipation is the result that the various thermodynamic functions of the sub-system do not only depend on the dissipation strength but depend as well on the prescription employed in their definition.

DOI
10.48550/arxiv.quant-ph/0601056

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The quantum thermodynamic behavior of small systems is investigated in presence of finite quantum dissipation. We consider the archetype cases of a damped harmonic oscillator and a free quantum Brownian particle. A main finding is that quantum dissipation helps to ensure the validity of the Third Law. For the quantum oscillator, finite damping replaces the zero-coupling result of an exponential suppression of the specific heat at low temperatures by a power-law behavior. Rather intriguing is the behavior of the free quantum Brownian particle. In this case, quantum dissipation is able to restore the Third Law: Instead of being constant down to zero temperature, the specific heat now vanishes proportional to temperature with an amplitude that is inversely proportional to the ohmic dissipation strength. A distinct subtlety of finite quantum dissipation is the result that the various thermodynamic functions of the sub-system do not only depend on the dissipation strength but depend as well on the prescription employed in their definition.
The quantum thermodynamic behavior of small systems is investigated in presence of finite quantum dissipation. We consider the archetype cases of a damped harmonic oscillator and a free quantum Brownian particle. A main finding is that quantum dissipation helps to ensure the validity of the Third Law. For the quantum oscillator, finite damping replaces the zero-coupling result of an exponential suppression of the specific heat at low temperatures by a power-law behavior. Rather intriguing is the behavior of the free quantum Brownian particle. In this case, quantum dissipation is able to restore the Third Law: Instead of being constant down to zero temperature, the specific heat now vanishes proportional to temperature with an amplitude that is inversely proportional to the ohmic dissipation strength. A distinct subtlety of finite quantum dissipation is the result that the various thermodynamic functions of the sub-system do not only depend on the dissipation strength but depend as well on the prescription employed in their definition.
We consider a free particle coupled with finite strength to a bath and investigate the evaluation of its specific heat. A harmonic oscillator bath of Drude type with cutoff frequency ω D is employed to model an ohmic friction force with dissipation strength γ. Two scenarios for obtaining specific heat are presented. The first one uses the measurement of the kinetic energy of the free particle, while the second one is based on the reduced partition function. Both descriptions yield results which are consistent with the Third Law of thermodynamics. Nevertheless, the two methods produce different results that disagree even in their leading quantum corrections at high temperatures. We also consider the regime where the cutoff frequency is smaller than the friction strength, i.e. ω D < γ. There, we encounter puzzling results at low temperatures where the specific heat based on the thermodynamic prescription becomes negative. This anomaly is rooted in an ill-defined density of states of the damped free particle, which assumes unphysical negative values when γ/ω D > 1.
Abstract This review provides a brief and quick introduction to the quantum Langevin equation for an oscillator, while focusing on the steady-state thermodynamic aspects. A derivation of the quantum Langevin equation is carefully outlined based on the microscopic model of the heat bath as a collection of a large number of independent quantum oscillators, the so-called independent-oscillator model. This is followed by a discussion on the relevant ‘weak-coupling’ limit. In the steady state, we analyze the quantum counterpart of energy equipartition theorem which has generated a considerable amount of interest in recent literature. The free energy, entropy, specific heat, and third law of thermodynamics are discussed for one-dimensional quantum Brownian motion in a harmonic well. Following this, we explore some aspects of dissipative diamagnetism in the context of quantum Brownian oscillators, emphasizing upon the role of confining potentials and also upon the environment-induced classical-quantum crossover. We discuss situations where the system-bath coupling is via the momentum variables by focusing on a gauge-invariant model of momentum-momentum coupling in the presence of a vector potential; for this problem, we derive the quantum Langevin equation and discuss quantum thermodynamic functions. Finally, the topic of fluctuation theorems is discussed (albeit, briefly) in the context of classical and quantum cyclotron motion of a particle coupled to a heat bath.
The Brownian motion of a quantum particle in a harmonic confining potential and coupled to harmonic quantum thermal bath is exactly solvable. Though this system presents at high temperatures a pedagogic example to explain the laws of thermodynamics, it is shown that at low enough temperatures the stationary state is non-Gibbsian due to an entanglement with the bath. In physical terms, this happens when the cloud of bath modes around the particle starts to play a nontrivial role, namely, when the bath temperature T is smaller than the coupling energy. Indeed, equilibrium thermodynamics of the total system, particle plus bath, does not imply standard equilibrium thermodynamics for the particle itself at low T. Various formulations of the second law are found to be invalid at low T. First, the Clausius inequality can be violated, because heat can be extracted from the zero point energy of the cloud of bath modes. Second, when the width of the confining potential is suddenly changed, there occurs a relaxation to equilibrium during which the entropy production is partly negative. In this process the energy put on the particle does not relax monotonically, but oscillates between particle and bath, even in the limit of strong damping. Third, for nonadiabatic changes of system parameters the rate of energy dissipation can be negative, and, out of equilibrium, cyclic processes are possible which extract work from the bath. Conditions are put forward under which perpetuum mobility of the second kind, having one or several work extraction cycles, enter the realm of condensed matter physics. Fourth, it follows that the equivalence between different formulations of the second law (e.g., those by Clausius and Thomson) can be violated at low temperatures. These effects are the consequence of quantum entanglement in the presence of the slightly off-equilibrium nature of the thermal bath, and become important when the characteristic quantum time scale variant Planck's over 2pi /k(B)T is larger than or comparable to other time scales of the system. They show that there is no general consensus between standard thermodynamics and quantum mechanics. The known agreements occur only due to the weak coupling limit, which does not pertain to low temperatures. Experimental setups for testing the effects are discussed.
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.