Open quantum systems play a central role in contemporary nanoscale technologies, including molecular electronics, quantum heat engines, quantum computation and information processing. A major theoretical challenge is to construct dynamical models that are simultaneously consistent with classical thermodynamics and complete positivity. In this work, we develop a framework that addresses this issue by extending classical stochastic dynamics to the quantum domain. We begin by formulating a generalized Langevin equation in which both friction and noise act symmetrically on the two Hamiltonian equations. From this, we derive a generalized Klein-Kramers equation expressed in terms of Poisson brackets, and we show that it admits the Boltzmann distribution as its stationary solution while satisfying the first and second laws of thermodynamics along individual trajectories. Applying canonical quantization to this classical framework yields two distinct quantum master equations, depending on whether the friction operators are taken to be Hermitian or non-Hermitian. By analyzing the dynamics of a harmonic oscillator, we determine the conditions under which these equations reduce to a Lindblad-type generator. Our results demonstrate that complete positivity is ensured only when friction and noise are included in both Hamiltonian equations, thus fully justifying the classical construction. Moreover, we find that the friction coefficients must satisfy the same positivity condition in both the Hermitian and non-Hermitian formulations, revealing a form of universality that transcends the specific operator representation. The formalism offers a versatile tool for deriving quantum versions of the thermodynamic laws and is directly applicable to a wide class of nonequilibrium nanoscale systems.
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arXiv admin note: text overlap with arXiv:2504.11938
Open quantum systems play a central role in contemporary nanoscale technologies, including molecular electronics, quantum heat engines, quantum computation and information processing. A major theoretical challenge is to construct dynamical models that are simultaneously consistent with classical thermodynamics and complete positivity. In this work, we develop a framework that addresses this issue by extending classical stochastic dynamics to the quantum domain. We begin by formulating a generalized Langevin equation in which both friction and noise act symmetrically on the two Hamiltonian equations. From this, we derive a generalized Klein-Kramers equation expressed in terms of Poisson brackets, and we show that it admits the Boltzmann distribution as its stationary solution while satisfying the first and second laws of thermodynamics along individual trajectories. Applying canonical quantization to this classical framework yields two distinct quantum master equations, depending on whether the friction operators are taken to be Hermitian or non-Hermitian. By analyzing the dynamics of a harmonic oscillator, we determine the conditions under which these equations reduce to a Lindblad-type generator. Our results demonstrate that complete positivity is ensured only when friction and noise are included in both Hamiltonian equations, thus fully justifying the classical construction. Moreover, we find that the friction coefficients must satisfy the same positivity condition in both the Hermitian and non-Hermitian formulations, revealing a form of universality that transcends the specific operator representation. The formalism offers a versatile tool for deriving quantum versions of the thermodynamic laws and is directly applicable to a wide class of nonequilibrium nanoscale systems.
Abstract Open quantum systems play a central role in current nanoscale technologies, such as molecular electronics, quantum heat engines, quantum computation and information processing. A major theoretical challenge is to construct dynamical models that are simultaneously consistent with classical thermodynamics and with the requirement of complete positivity of quantum evolution. In this work we develop a framework that addresses this issue by systematically extending classical stochastic dynamics to the quantum domain. We begin by formulating a generalized Langevin equation in which both friction and noise act symmetrically on the two Hamiltonian equations. From this, we derive a generalized Klein–Kramers equation expressed in terms of Poisson brackets, and we show that it admits the Boltzmann distribution as its stationary solution while fulfilling the first and second laws of thermodynamics along individual trajectories. Applying canonical quantization to this classical framework yields two distinct quantum master equations, depending on whether the friction operators are taken to be Hermitian or non-Hermitian. By analyzing the dynamics of a harmonic oscillator, we determine the conditions under which these equations reduce to a Lindblad-type generator. Our results demonstrate that complete positivity is ensured only when friction and noise are included in both Hamiltonian equations, fully justifying the classical construction. Moreover, we find that the friction coefficients must adhere to the same positivity condition in both the Hermitian and non-Hermitian formulations, revealing a form of universality that transcends the specific operator representation. The formalism developed here presents a thermodynamically consistent and completely positive quantum extension of classical stochastic mechanics. It offers a versatile tool for deriving quantum versions of thermodynamic laws and is directly applicable to a broad class of non-equilibrium nanoscale systems of current theoretical and technological interest.
Abstract The theory of open quantum systems plays a fundamental role in several scientific and technological disciplines, from quantum computing and information science to molecular electronics and quantum thermodynamics. Despite its widespread relevance, a rigorous formulation of quantum dissipation in conjunction with thermal noise remains a topic of active research. In this work, we establish a formal correspondence between classical stochastic thermodynamics, in particular the Fokker–Planck and Klein–Kramers equations, and the quantum master equation. Building on prior studies of multiplicative noise in classical stochastic differential equations, we demonstrate that thermal noise at the quantum level manifests as a multidimensional geometric stochastic process. By applying canonical quantization, we introduce a novel Hermitian dissipation operator that serves as a quantum analogue of classical viscous friction. This operator allows for a well-defined expression of heat exchange between a system and its environment, enabling the formulation of an alternative quantum equipartition theorem. Our framework ensures a precise energy balance that aligns with the first law of thermodynamics and an entropy balance consistent with the second law. The theoretical formalism is applied to two prototypical quantum systems, the harmonic oscillator and a particle in an infinite potential well, for which it provides new insights into nonequilibrium thermodynamics at the quantum scale. Our results advance the understanding of dissipation in quantum systems and establish a foundation for future studies on stochastic thermodynamics in the quantum domain.
Within the framework of the quantum-statistical approach, utilizing both non-Hermitian Hamiltonian and Lindblad’s jump operators, one can derive various generalizations of the von Neumann equation for reduced density operators, also known as hybrid master equations. If one considers the evolution of pure states only, i.e., disregarding the coherence between states and spontaneous transitions from pure to mixed states, then one can resort to quantum-mechanical equations of the Schrödinger type. We derive them from the hybrid master equations and study their main properties, which indicate that our equations have a larger range of applicability compared to other generalized Schrödinger equations proposed hitherto. Among other features, they can describe not only systems which remain in the stationary eigenstates of the Hamiltonian as time passes, but also those which evolve from those eigenstates. As an example, we consider a simple but important model, a quantum harmonic oscillator driven by both Hamiltonian and non-Hamiltonian terms, and derive its classical limit, which turns out to be the damped harmonic oscillator. Using this model, we demonstrate that the effects of dissipative environments of different types can cancel each other, thus resulting in an effectively dissipation-free classical system. Another discussed phenomenon is whether a non-trivial quantum system can reduce to a classical system in free motion, i.e., without experiencing any classical Newtonian forces. This uncovers a large class of quantum-mechanical non-Hamiltonian systems whose dynamics are not determined by conventional mechanics’ potentials and forces, but rather come about through quantum statistical effects caused by the system’s environment.
In the frames of classical mechanics the generalized Langevin equation is derived for an arbitrary mechanical subsystem coupled to the harmonic bath of a solid. A time-acting temperature operator is introduced for the quantum Klein-Kramers and Smoluchowski equations, accounting for the effect of the quantum thermal bath oscillators. The model of Brownian emitters is theoretically studied and the relevant evolutionary equations for the probability density are derived. The Schrodinger equation is explained via collisions of the target point particles with the quantum force carriers, transmitting the fundamental interactions between the point particles. Thus, electrons and other point particles are no waves and the wavy chapter of quantum mechanics originated for the force carriers. A stochastic Lorentz-Langevin equation is proposed to describe the underlaying Brownian-like motion of the point particles in quantum mechanics. Considering the Brownian dynamics in the frames of the Bohmian mechanics, the density functional Bohm-Langevin equation is proposed, and the relevant Smoluchowski-Bohm equation is derived. A nonlinear master equation is proposed by proper quantization of the classical Klein-Kramers equation. Its equilibrium solution in the exact canonical Gibbs density operator, while the well-known Caldeira-Leggett equation is simply a linearization at high temperature. In the case of a free quantum Brownian particles, a new law for the spreading of the wave packet it discovered, which represents the quantum generalization of the classical Einstein law of Brownian motion. A new projector operator is proposed for the collapse of the wave function of a quantum particle moving in a classical environment. Its application results in dissipative Schrodinger equations, as well as in a new form of dissipative Liouville equation in classical mechanics.
A consistent theory of non-equilibrium thermodynamics for Markovian open quantum systems has been developed in the late seventies in analogy with Classical Irreversible Thermodynamics. The time-evolution of these open systems is usually described by means of effective master equations in Lindblad form, that turn out to be reliable when there is a separation of time-scales between system and environment, such that memory effects are negligible and the so-called Markovian approximation is justified. In this framework, the variations of energy and entropy in the system are consistently described, distinguishing between heat and work contributions and providing a statement of the second law of thermodynamics as positivity of the entropy production.\nHowever, there is empirical evidence that many physical systems like photosynthetic complexes,\nopto-mechanical resonators and superconducting qubits, just to mention a few, experience more general non-Markovian dynamics. The formulation of the laws of thermodynamics in a non-Markovian setting is matter of current research and represents the main topic of the present work. As a first step, we show that the entropy production defined as in the Markovian case can be negative for a class of non-Markovian dynamics. We argue that this outcome should not be interpreted as a violation of the second law of thermodynamics because the environment must be explicitly taken into account in the balance of entropy in the non-Markovian setting. In order to justify this claim we adopt a more general point of view, studying a closed bipartite quantum system, such that each of the two subsystems plays the role of a finite environment out of equilibrium for the other one. We concentrate on the balance of energy first and construct an effective Hamiltonian for each subsystem using physically reasonable requirements; then we define heat and work as in the standard Markovian treatment, with the effective Hamiltonian replacing the free Hamiltonian. It turns out that, in our framework, the work power is perfectly balanced between subsystems, while the correlations can store a part of energy locally inaccessible and exchange it with both subsystems in the form of heat.\nConcerning the balance of entropy, a quite general formulation of the second law of thermodynamics can be given as follows: under the assumption of a factorized initial state for the compound system, the sum of the total variations of the entropies in the two subsystems is always nonnegative. We show with an explicit example that this general formulation does not correspond to the statement presented in the framework of Markovian master equations, which should not be considered a priori the second law of thermodynamics.\nIn the last part of the thesis we concentrate of the so-called fluctuation relations, that are results extending the thermodynamic formalism beyond the behavior of average quantities. After reviewing the main theoretical outcomes, such as the Jarzynski equality and the Crooks fluctuation theorem, we describe a proposal to access experimentally the work performed on an ensemble of diatomic molecules by a time-dependent electric field coupled with their vibrational degree of freedom. This procedure could then be used to test the quantum Jarzynski equality. With respect to the results so far appeared in the literature, in which the left-hand side of the equality is inferred from an experiment and the right-hand side is computed according to a model, in our proposed setting we should be able to estimate from the experiment both the left-hand side and the right-hand side of the equality, independently.
All physical theories should obey the second law of thermodynamics. However, existing proposals to describe the dynamics of hybrid classical-quantum systems either violate the second law or lack a proof of its existence. Here, we rectify this by studying classical-quantum dynamics that are (1) linear and completely positive and (2) preserve the thermal state of the classical-quantum system. We first prove that such dynamics necessarily satisfy the second law. We then show how these dynamics may be constructed, proposing dynamics that generalize the standard Langevin and Fokker-Planck equations for classical systems in thermal environments to include backreaction from a quantum degree of freedom. Deriving necessary and sufficient conditions for completely positive, linear, and continuous classical-quantum dynamics to satisfy detailed balance, we find this property satisfied by our dynamics. To illustrate the formalism and its applications, we introduce two models. The first is an analytically solvable model of an overdamped classical system coupled to a quantum two-level system, which we use to study the total entropy production in both quantum system and classical measurement apparatus during a quantum measurement. The second describes an underdamped classical-quantum oscillator system subject to friction, which we numerically demonstrate exhibits thermalization in the adiabatic basis, showing the relevance of our dynamics for the mixed classical-quantum simulation of molecules.