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arXiv:1610.09068

Quantum fluctuation theorems and work-energy relationships with due regard for convergence, dissipation and irreversibility

Carolyne M. Van Vliet

Published Oct 28, 2016• 0 citations
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Abstract

Firstly the fluctuation theorems (FT) for expended work in a driven nonequilibrium system, isolated or thermostatted, together with the ensuing Jarzynski work-energy (W-E) relationships, will be discussed and reobtained. Secondly, the fluctuation theorems for entropy flow will be reconsidered. Our treatment will be fully quantum-statistical, being an ex-tension of our previous research reported in Phys. Rev. E (2012), and will avoid the deficiencies that afflicted previous works such as: arguments based on classical trajectories in phase space, a reliance on the 'pure' von Neumann equation or 'non-reduced' Heisenberg operators, or other departures from the general tenets spelled out by Lindblad and others (e.g. Breuer and Petruccione) such as stochastic 'jump-induced' random trajectories. While a number of relationships from such previous works will still be employed, our Markov probability $P(σ_f,t_f|σ_0,t_0)$ shall only denote the two state-points, with no reference whatsoever to stochastic trajectories, these being meaningless in a quantum description.

DOI
10.48550/arxiv.1610.09068

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Firstly the fluctuation theorems (FT) for expended work in a driven nonequilibrium system, isolated or thermostatted, together with the ensuing Jarzynski work-energy (W-E) relationships, will be discussed and reobtained. Secondly, the fluctuation theorems for entropy flow will be reconsidered. Our treatment will be fully quantum-statistical, being an ex-tension of our previous research reported in Phys. Rev. E (2012), and will avoid the deficiencies that afflicted previous works such as: arguments based on classical trajectories in phase space, a reliance on the 'pure' von Neumann equation or 'non-reduced' Heisenberg operators, or other departures from the general tenets spelled out by Lindblad and others (e.g. Breuer and Petruccione) such as stochastic 'jump-induced' random trajectories. While a number of relationships from such previous works will still be employed, our Markov probability P(σf,tf∣σ0,t0)P(σ_f,t_f|σ_0,t_0)P(σf​,tf​∣σ0​,t0​) shall only denote the two state-points, with no reference whatsoever to stochastic trajectories, these being meaningless in a quantum description.
Firstly the fluctuation theorems (FT) for expended work in a driven nonequilibrium system, isolated or thermostatted, together with the ensuing Jarzynski work-energy (W-E) relationships, will be discussed and reobtained. Secondly, the fluctuation theorems for entropy flow will be reconsidered. Our treatment will be fully quantum-statistical, being an ex-tension of our previous research reported in Phys. Rev. E (2012), and will avoid the deficiencies that afflicted previous works such as: arguments based on classical trajectories in phase space, a reliance on the 'pure' von Neumann equation or 'non-reduced' Heisenberg operators, or other departures from the general tenets spelled out by Lindblad and others (e.g. Breuer and Petruccione) such as stochastic 'jump-induced' random trajectories. While a number of relationships from such previous works will still be employed, our Markov probability P(σf,tf∣σ0,t0)P(\sigma_f,t_f|\sigma_0,t_0)P(σf​,tf​∣σ0​,t0​) shall only denote the two state-points, with no reference whatsoever to stochastic trajectories, these being meaningless in a quantum description.
We expand on the ideas developed by C. Jarzynski in Physica A 552, 122077 (2020), where an integral fluctuation theorem was derived with the aim of obtaining thermodynamic inequalities stronger than those implied by the Jarzynski equality. Restricting ourselves to the quantum setting, we derive the corresponding detailed fluctuation theorem and additional detailed and integral fluctuation theorems; we also provide a clear physical interpretation of the stochastic quantities defined in the previous reference. Furthermore, we show that their averages are given by the nonadiabaticity parameter (i.e., the relative entropy between the final state after a finite-time driving protocol and the corresponding adiabatically evolved state) and the excess work (also known as inner friction). We elaborate on the inequalities derived from the fluctuation theorems and discuss their connection to irreversibility and formulations of the Second Law.
In thermodynamics, entropy production and work quantify irreversibility and the consumption of useful energy, respectively, when a system is driven out of equilibrium. For quantum systems, these quantities can be identified at the stochastic level by unravelling the system's evolution in terms of quantum jump trajectories. We here derive a general formula for computing the joint statistics of work and entropy production in Markovian driven quantum systems, whose instantaneous steady states are of Gibbs form. If the driven system remains close to the instantaneous Gibbs state at all times, then we show that the corresponding two-variable cumulant generating function implies a joint detailed fluctuation theorem so long as detailed balance is satisfied. As a corollary, we derive a modified fluctuation-dissipation relation (FDR) for the entropy production alone, applicable to transitions between arbitrary steady states, and for systems that violate detailed balance. This FDR contains a term arising from genuinely quantum fluctuations, and extends an analogous relation from classical thermodynamics to the quantum regime.
We explore some aspects of nonequilibrium statistical mechanics of classical and quantum systems. Two chapters are devoted to fluctuation theorems which were originally derived for classical systems. The main challenge in formulating them in quantum mechanics is the fact that fundamental quantities of interest, like work, are defined via the classical concept of a phase space trajectory. We utilize the decoherent histories conceptual framework, in which classical trajectories emerge in quantum mechanics as a result of coarse graining, and provide a first-principles analysis of the nonequilibrium work relation of Jarzynski and Crooks's fluctuation theorem for a quantum system interacting with a general environment based on the quantum Brownian motion (QBM) model. We indicate a parameter range at low temperatures where the theorems might fail in their original form. Fluctuation theorems of Jarzynski and Crooks for systems obeying classical Hamiltonian dynamics are derived under the assumption that the initial conditions are sampled from a canonical ensemble, even though the equilibrium state of an isolated system is typically associated with the microcanonical ensemble. We address this issue through an exact analysis of the classical Brownian motion model. We argue that a stronger form of ensemble equivalence than usually discussed in equilibrium statistical mechanics is required for these theorems to hold in the infinite environment limit irrespective of the ensemble used, and proceed to prove it for this model. An exact expression for the probability distribution of work is obtained for finite environments. Intuitively one expects a system to relax to an equilibrium state when brought into contact with a thermal environment. Yet it is important to have rigorous results that provide conditions for equilibration and characterize the equilibrium state. We consider the dynamics of open quantum systems using the Langevin and master equations and rigorously show that under fairly general conditions quantum systems interacting with a heat bath relax to the equilibrium state defined as the reduced thermal state of the system plus environment, even in the strong coupling regime. Our proof is valid to second-order in interaction strength for general systems and exact for the linear QBM model, for which we also show the equivalence of multi-time correlations. In the final chapter we give a sampling of our investigations into macroscopic quantum phenomena. We work out in detail a specific example of how and under what conditions the center of mass (CoM) coordinate of a macroscopic object emerges as the relevant degree of freedom. Interaction patterns are studied in terms of the couplings they induce between the CoM and relative coordinates of two macroscopic objects. We discuss the implications of these interaction patterns on macroscopic entanglement.
In this paper we present a first-principles analysis of the nonequilibrium work distribution and the free energy difference of a quantum system interacting with a general environment (with arbitrary spectral density and for all temperatures) based on a well-understood microphysics (quantum Brownian motion) model under the conditions stipulated by the Jarzynski equality [Jarzynski, Phys. Rev. Lett. 78, 2690 (1997)] and Crooks' fluctuation theorem [Crooks, Phys. Rev. E 60, 2721 (1999)] (in short, fluctuation theorems, FTs). We use the decoherent histories conceptual framework to explain how the notion of trajectories in a quantum system can be made viable and use the environment-induced decoherence scheme to assess the strength of noise that could provide sufficient decoherence to warrant the use of trajectories to define work in open quantum systems. From the solutions to the Langevin equation governing the stochastic dynamics of such systems we were able to produce formal expressions for these quantities entering in the FTs and from them prove explicitly the validity of the FTs at the high temperature limit. At low temperatures our general results would enable one to identify the range of parameters where FTs may not hold or need be expressed differently. We explain the relation between classical and quantum FTs and the advantage of this microphysics open-system approach over the phenomenological modeling and energy-level calculations for substitute closed quantum systems.
Markovian quantum master equations (MQMEs) were established nearly half a century ago. They have often been used in the study of irreversible thermodynamics. However, the previous results were mainly concerned about ensemble averages; the stochastic thermodynamics of these systems went unnoticed for a very long time. This situation remained unchanged until a variety of fluctuation theorems in classical and quantum regimes were found in the past two decades. In this paper, we systematically summarize the current understanding on the stochastic heat and work in MQMEs using two distinct strategies. One strategy is to treat the system and its surrounding heat bath as a closed quantum system, to suppose that the evolution of the composite system is unitary under a time-dependent total Hamiltonian and to define the heat and work as the changes in energy by applying two energy measurements scheme to the composite system. The other strategy is to unravel these MQMEs into random quantum jump trajectories (QJTs) and to define the stochastic heat and work along the individual trajectories. Many important physical concepts, mathematical techniques, and fluctuation theorems at different descriptive levels are given in as detailed a manner as possible. We also use concrete models to illustrate these results.