Framework Of Quantum Thermodynamics Research Articles

Predicting Ion Sequestration in Charged Polymers with the Steepest-Entropy-Ascent Quantum Thermodynamic Framework.

The steepest-entropy-ascent quantum thermodynamic framework is used to investigate the effectiveness of multi-chain polyethyleneimine-methylenephosphonic acid in sequestering rare-earth ions (Eu3+) from aqueous solutions. The framework applies a thermodynamic equation of motion to a discrete energy eigenstructure to model the binding kinetics of europium ions to reactive sites of the polymer chains. The energy eigenstructure is generated using a non-Markovian Monte Carlo model that estimates energy level degeneracies. The equation of motion is used to determine the occupation probability of each energy level, describing the unique path through thermodynamic state space by which the polymer system sequesters rare-earth ions from solution. A second Monte Carlo simulation is conducted to relate the kinetic path in state space to physical descriptors associated with the polymer, including the radius of gyration, tortuosity, and Eu-neighbor distribution functions. These descriptors are used to visualize the evolution of the polymer during the sequestration process. The fraction of sequestered Eu3+ ions depends upon the total energy of the system, with lower energy resulting in greater sequestration. The kinetics of the overall sequestration are dependent on the steepest-entropy-ascent principle used by the equation of motion to generate a unique kinetic path from an initial non-equilibrium state.

Fluctuation theorems for genuine quantum mechanical regimes

Of indisputable relevance for nonequilibrium thermodynamics, fluctuations theorems have been generalized to the framework of quantum thermodynamics, with the notion of work playing a key role in such contexts. The typical approach consists of treating work as a stochastic variable and the acting system as an eminently classical device with a deterministic dynamics. Inspired by technological advances in the field of quantum machines, here we look for corrections to work fluctuations theorems when the acting system is allowed to enter the quantum domain. This entails including the acting system in the dynamics and letting it share a nonclassical state with the system acted upon. Moreover, favoring a mechanical perspective to this program, we employ a concept of work observable. For simplicity, we choose as theoretical platform the autonomous dynamics of a two-particle system with an elastic coupling. For some specific processes, we derive several fluctuation theorems within both the quantum and classical statistical arenas. In the quantum results, we find that, along with entanglement and quantum coherence, aspects of inertia also play a significant role since they regulate the route to mechanical equilibrium.

Operational Interpretation of Quantum Fisher Information in Quantum Thermodynamics.

In the framework of quantum thermodynamics preparing a quantum system in a general state requires the consumption of two distinct resources, namely, work and energetic coherence. It has been shown that the work cost of preparing a quantum state is determined by its free energy. Considering a similar setting, here we determine the coherence cost of preparing a general state when there are no restrictions on work consumption. More precisely, the coherence cost is defined as the minimum rate of consumption of systems in a pure coherent state, that is needed to prepare copies of the desired system. We show that the coherence cost of any system is determined by its quantum Fisher information about the time parameter, hence introducing a new operational interpretation of this central quantity of quantum metrology. Our resource-theoretic approach also reveals a previously unnoticed connection between two fundamental properties of quantum Fisher information.

Thermodynamics of Minimal Coupling Quantum Heat Engines

The minimal-coupling quantum heat engine is a thermal machine consisting of an explicit energy storage system, heat baths, and a working body, which alternatively couples to subsystems through discrete strokes --- energy-conserving two-body quantum operations. Within this paradigm, we present a general framework of quantum thermodynamics, where a work extraction process is fundamentally limited by a flow of non-passive energy (ergotropy), while energy dissipation is expressed through a flow of passive energy. It turns out that small dimensionality of the working body and a restriction only to two-body operations make the engine fundamentally irreversible. Our main result is finding the optimal efficiency and work production per cycle within the whole class of irreversible minimal-coupling engines composed of three strokes and with the two-level working body, where we take into account all possible quantum correlations between the working body and the battery. One of the key new tools is the introduced ``control-marginal state" --- one which acts only on a working body Hilbert space, but encapsulates all features regarding work extraction of the total working body-battery system. In addition, we propose a generalization of the many-stroke engine, and we analyze efficiency vs extracted work trade-offs, as well as work fluctuations after many cycles of the running of the engine.

Kinetic pathways of ordering and phase separation using classical solid state models within the steepest-entropy-ascent quantum thermodynamic framework

The kinetics of ordering and concurrent ordering and phase separation are analyzed with an equation of motion initially developed to account for dissipative processes in quantum systems. A reduced-order energy eigenstructure, or pseudo-eigenstructure, is constructed from a static concentration wave method to describe the configuration-dependent energy in a binary alloy. This pseudo-eigenstructure is used in conjunction with an equation of motion that follows steepest entropy ascent to calculate the kinetic path that leads to ordering and phase separation in a series of hypothetical alloys. By adjusting the thermodynamic solution parameters, it is demonstrated that the model can predict: (a) the stable equilibrium state, (b) the unique thermodynamic path and kinetics of continuous or discontinuous ordering, and (c) the kinetics of concurrent processes involving simultaneous ordering and phase separation.

Predicting continuous and discontinuous phase decompositions using steepest-entropy-ascent quantum thermodynamics

The decomposition kinetics of a solid solution into separate phases are analyzed with an equation of motion initially developed to account for dissipative processes in quantum systems. This equation and the steepest-entropy-ascent quantum thermodynamic framework of which it is a part make it possible to track kinetic processes in systems at nonequilibrium while retaining the framework of classical equilibrium thermodynamics. The general equation of motion is particularized for the case of the decomposition of a binary alloy, and a solution model is used to build an approximate energy eigenstructure, or pseudoeigenstructure, for the alloy system. This equation is then solved with the pseudoeigenstructure to obtain a unique reaction path and the decomposition kinetics of the alloy. For a hypothetical solid solution with a miscibility gap at low temperatures, the conditions under which this framework predicts a continuous transformation path (spinodal decomposition) or a discontinuous one (nucleation and growth) are demonstrated.

Methodology of an application of the steepest-entropy-ascent quantum thermodynamic framework to physical phenomena in materials science

Steepest-entropy-ascent quantum thermodynamics, or SEAQT, is a unified approach of quantum mechanics and thermodynamics that avoids many of the inconsistencies that can arise between the two theories. Given a set of energy eigenlevels, i.e., energy eigenstructure, accessible to a given physical system, SEAQT predicts the unique kinetic path from any initial non-equilibrium state to stable equilibrium by solving a master equation that directs the system along the path of steepest entropy ascent. There are no intrinsic limitations on the length and time scales the method can treat so it is well-suited for calculations where the dynamics over multiple spacial scales need to be taken into account within a single framework. In this paper, the theoretical framework and its advantages are described, and several applications are presented to illustrate the use of the SEAQT equation of motion and the construction of a simplified, reduced-order, energy eigenstructure.

Experimental demonstration of work fluctuations along a shortcut to adiabaticity with a superconducting Xmon qubit

In a ‘shortcut to adiabaticity’ (STA) protocol, the counter-diabatic Hamiltonian, which suppresses the non-adiabatic transition of a reference ‘adiabatic’ trajectory, induces a quantum uncertainty of the work cost in the framework of quantum thermodynamics. Following a theory derived recently (Funo et al 2017 Phys. Rev. Lett. 118 100602), we perform an experimental measurement of the STA work statistics in a high-quality superconducting Xmon qubit. Through the frozen-Hamiltonian and frozen-population techniques, we experimentally realize the two-point measurement of the work distribution for given initial eigenstates. Our experimental statistics verify (i) the conservation of the average STA work and (ii) the equality between the STA excess of work fluctuations and the quantum geometric tensor.

DFT-inspired methods for quantum thermodynamics

In the framework of quantum thermodynamics, we propose a method to quantitatively describe thermodynamic quantities for out-of-equilibrium interacting many-body systems. The method is articulated in various approximation protocols which allow to achieve increasing levels of accuracy, it is relatively simple to implement even for medium and large number of interactive particles, and uses tools and concepts from density functional theory. We test the method on the driven Hubbard dimer at half filling, and compare exact and approximate results. We show that the proposed method reproduces the average quantum work to high accuracy: for a very large region of parameter space (which cuts across all dynamical regimes) estimates are within 10% of the exact results.

Steepest-entropy-ascent nonequilibrium quantum thermodynamic framework to model chemical reaction rates at an atomistic level.

The steepest entropy ascent (SEA) dynamical principle provides a general framework for modeling the dynamics of nonequilibrium (NE) phenomena at any level of description, including the atomistic one. It has recently been shown to provide a precise implementation and meaning to the maximum entropy production principle and to encompass many well-established theories of nonequilibrium thermodynamics into a single unifying geometrical framework. Its original formulation in the framework of quantum thermodynamics (QT) assumes the simplest and most natural Fisher-Rao metric to geometrize from a dynamical standpoint the manifold of density operators, which represent the thermodynamic NE states of the system. This simplest SEAQT formulation is used here to develop a general mathematical framework for modeling the NE time evolution of the quantum state of a chemically reactive mixture at an atomistic level. The method is illustrated for a simple two-reaction kinetic scheme of the overall reaction F+H_{2}⇔HF+F in an isolated tank of fixed volume. However, the general formalism is developed for a reactive system subject to multiple reaction mechanisms. To explicitly implement the SEAQT nonlinear law of evolution for the density operator, both the energy and the particle number eigenvalue problems are set up and solved analytically under the dilute gas approximation. The system-level energy and particle number eigenvalues and eigenstates are used in the SEAQT equation of motion to determine the time evolution of the density operator, thus effectively describing the overall kinetics of the reacting system as it relaxes toward stable chemical equilibrium. The predicted time evolution in the near-equilibrium limit is compared to the reaction rates given by a standard detailed kinetic model so as to extract the single time constant needed by the present SEA model.

From single-shot towards general work extraction in a quantum thermodynamic framework

This paper considers work extraction from a quantum system to a work storage system (or weight) following Horodecki and Oppenheim (2013 Nat. Commun. 4 2059). An alternative approach is here developed that relies on the comparison of subspace dimensions without a need to introduce thermo-majorization used previously. Optimal single shot work for processes where a weight transfers from (a) a single energy level to another single energy level is then re-derived. In addition we discuss the final state of the system after work extraction and show that the system typically ends in its thermal state, while there are cases where the system is only close to it. The work of formation in the single level transfer setting is also re-derived. The approach presented now allows the extension of the single shot work concept to work extraction (b) involving multiple final levels of the weight. A key conclusion here is that the single shot work for case (a) is appropriate only when a resonance of a particular energy is required. When wishing to identify ‘work extraction’ with finding the weight in a specific available energy or any higher energy a broadening of the single shot work concept is required. As a final contribution we consider transformations of the system that (c) result in general weight state transfers. Introducing a transfer-quantity allows us to formulate minimum requirements for transformations to be at all possible in a thermodynamic framework. We show that choosing the free energy difference of the weight as the transfer-quantity one recovers various single shot results including single level transitions (a), multiple final level transitions (b), and recent results on restricted sets of multi-level to multi-level weight transfers.

Explanation of the Gibbs paradox within the framework of quantum thermodynamics

The issue of the Gibbs paradox is that when considering mixing of two gases within classical thermodynamics, the entropy of mixing appears to be a discontinuous function of the difference between the gases: it is finite for whatever small difference, but vanishes for identical gases. The resolution offered in the literature, with help of quantum mixing entropy, was later shown to be unsatisfactory precisely where it sought to resolve the paradox. Macroscopic thermodynamics, classical or quantum, is unsuitable for explaining the paradox, since it does not deal explicitly with the difference between the gases. The proper approach employs quantum thermodynamics, which deals with finite quantum systems coupled to a large bath and a macroscopic work source. Within quantum thermodynamics, entropy generally loses its dominant place and the target of the paradox is naturally shifted to a decrease of the maximally available work before and after mixing (mixing ergotropy). In contrast to entropy this is an unambiguous quantity. For almost identical gases the mixing ergotropy continuously goes to zero, thus resolving the paradox. In this approach the concept of "difference between the gases" gets a clear operational meaning related to the possibilities of controlling the involved quantum states. Difficulties which prevent resolutions of the paradox in its entropic formulation do not arise here. The mixing ergotropy has several counterintuitive features. It can increase when less precise operations are allowed. In the quantum situation (in contrast to the classical one) the mixing ergotropy can also increase when decreasing the degree of mixing between the gases or when decreasing their distinguishability. These points go against a direct association of physical irreversibility with lack of information.