Activation/deactivation by inelastic collisions have been extensively studied at unimolecular reactions in gas phase where they are crucial for equilibration. As equilibration means an increase of entropy, the mechanism can also be considered responsible for entropy production. Theoretical treatments show a remarkable agreement with experiments. They rest upon the assumption of stochastic quantum transitions. Under this premise, master equations have been used that are known to deliver equilibria and entropy production. Here we examine the hypothesis that the ubiquitous inelastic interactions in gas and liquid phase may represent a source of entropy beyond chemical reactions, rotational activation/deactivation being the prevailing mechanism in gas dynamics at room temperature. For a quantum mechanical two-state model the master equations are formulated which yield entropy production and equilibration in translational degrees of freedom until, at conserved energy, a stationary Maxwell-Boltzmann distribution is reached. The relaxation rates show features that can be checked by monitoring thermal relaxation in gas phase. Depending on the composition, first or second order processes are predicted. The temperature dependence is determined by the activation energy of the lowest transition. Thus, experimental verification will allow to decide to which extent this hypothesis describes thermal relaxation. It would support a connection between the macroscopic second law of thermodynamics and the microscopic stochastic collapse in quantum mechanics, both experimentally secured facts which in theory emerge as special elements beyond Hamiltonian dynamics. It is also shown that inelastic collisions are connected with velocity-dependent forces and result in a new analog of the Fokker-Planck equation where they replace Langevin dynamics as a non-Hamiltonian dissipative mechanism.
Activation/deactivation by inelastic collisions have been extensively studied at unimolecular reactions in gas phase where they are crucial for equilibration. As equilibration means an increase of entropy, the mechanism can also be considered responsible for entropy production. Theoretical treatments show a remarkable agreement with experiments. They rest upon the assumption of stochastic quantum transitions. Under this premise, master equations have been used that are known to deliver equilibria and entropy production. Here we examine the hypothesis that the ubiquitous inelastic interactions in gas and liquid phase may represent a source of entropy beyond chemical reactions, rotational activation/deactivation being the prevailing mechanism in gas dynamics at room temperature. For a quantum mechanical two-state model the master equations are formulated which yield entropy production and equilibration in translational degrees of freedom until, at conserved energy, a stationary Maxwell-Boltzmann distribution is reached. The relaxation rates show features that can be checked by monitoring thermal relaxation in gas phase. Depending on the composition, first or second order processes are predicted. The temperature dependence is determined by the activation energy of the lowest transition. Thus, experimental verification will allow to decide to which extent this hypothesis describes thermal relaxation. It would support a connection between the macroscopic second law of thermodynamics and the microscopic stochastic collapse in quantum mechanics, both experimentally secured facts which in theory emerge as special elements beyond Hamiltonian dynamics. It is also shown that inelastic collisions are connected with velocity-dependent forces and result in a new analog of the Fokker-Planck equation where they replace Langevin dynamics as a non-Hamiltonian dissipative mechanism.
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.
We consider the temporal evolution of the entropy S of an isolated system from an initial non-equilibrium state 2· of entropy S = S i to the equilibrium state of maximum entropy S = S max > S i. The application of usual density matrix theory of quantum mechanics leads us to the surprising result P = dS/dt = 0. The entropy does not change in time. This result is valid in case of the equilibrium state. However it is wrong for a non-equilibrium state, because the entropy of the isolated system could not spontaneously increase from S i to S max by entropy production P > 0. This contradicts the second law of thermodynamics. We avoid this discrepancy by changing from quantum mechanics to quantum thermodynamics. Now the entropy production P = dS/dt and the time t are the relevant observables. In order to treat the temporal development of S and P, we at first prepare an initial state i of entropy production P i at time t < 0. Subsequently at ϑ t ≥ 0 the initial state i interacts with a continuum of final states f, which transfers the entropy production from i to f. The temporal evolution of the entropy production P(t) of our system is treated by means of the time-dependent perturbation theory. For that reason we split the operator of entropy production P = P 0 + W into two parts. The operator P 0 describes the unperturbed basic vectors of entropy production | i > and | f >, while the perturbation operator W determines the interaction between | i > and | f >. We expand the time-dependent state function < t | ψ > of the isolated system into the complete set of stationary eigenvectors | i > and | f > and calculate the time-dependent expansion coefficients c i(t) and c(f, t) by means of the dynamic equation of quantum thermodynamics − i k (d/dt) < t | ψ > = < t | P | ψ >. Here k means the Boltzmann constant, which is characteristic of quantum thermodynamics and represents the atomic entropy unit. The expansion coefficients are given by a system of coupled differential equations, from which we deduce an integral-differential equation for the coefficient c i(t) of the initial state i. Unfortunately it has been impossible to obtain an analytic solution of the complicated equation. However approximations are available. Accordingly, in the vicinity of the equilibrium state, the probability of still finding the initial state i of entropy production P i at time t is given by ω i(t) = | c i(t) |2 = exp (−Lt). The rate constant L ≥ σ depends on the density ρ(P f) of final states f of entropy production P f near by P i, and on the squared modulus of the perturbation matrix elements W if = < i | W | f >, which determines the interaction between | i > and | f >. The entropy production P(t) = P i ω i(t) = P i exp (−ϑLt) of the isolated system decreases exponentially and irreversibly with proceeding time t. Its rate-determining step is the transfer of entropy production from i to f. The integral over the entropy production of the final states f vanishes. Therefore the continuum states f do not contribute to the total entropy production P(t). The temporal evolution of the entropy S(t) can easily be calculated by integration of P(t). In conclusion, the entropy production of a non-equilibrium state is finite P(t) > 0 and only vanishes in the case of the equilibrium state P(∞) = 0. Thus, quantum thermodynamics agrees with the second law of thermodynamics.
Thermodynamics is a phenomenological theory describing the energy conversion of work and heat. At its origins thermodynamics was developed in order to understand and improve heat engines. In conventional thermodynamics, however, only such processes are completely describable which are slow enough to keep the system of interest in an equilibrium state with its thermal environment at all times. On the contrary, all real physical processes are accompanied by non-equilibrium phenomena. These are mathematically described with the help of the irreversible entropy production, i.e. the dissipated work divided by the temperature of the bath. The second law of thermodynamics merely states that the irreversible entropy production is on average always positive. The modern trend of miniaturization, however, leads to smaller and smaller devices. On short length scales thermal noise as well as quantum fluctuations become important. Thus, usual thermodynamic quantities as work and heat acquire stochastic nature. Moreover, in the quantum regime a completely new theory had to be invented, since classical notions of work and heat are no longer valid. The present dissertation contributes to this prevailing field by the derivation of analytical expressions for the entropy production in open and closed quantum system far from thermal equilibrium. The theoretical treatment is motivated by an experimental point of view. The obtained results were derived from the reduced dynamics of the quantum mechanical system, which may be coupled to a thermal bath. To this end, it was dealt with methods and approaches of statistical physics, conventional thermodynamics, quantum information theory and the theory of open quantum systems. In this dissertation the most important physical systems are treated. First, an isolated system is considered before later on a heat bath is included. The limit of weak as well as of strong coupling are analyzed in detail. For isolated systems it turns out that a geometric approach is able to capture the thermodynamic properties, completely. To this end, the irreversible entropy production is sharply estimated from below by the angle between the real non-equilibrium state and the corresponding equilibrium one. Further, it is shown that the Heisenberg uncertainty relation for energy and time can be formulated more precisely in terms of that angle. As experimental system cold ion traps are introduced, in which the theoretical predictions can be verified. For weakly coupled systems, then, the irreversible entropy production is identified and a fluctuation theorem is derived by merely thermodynamic arguments. As experimental system we, again, propose the cold ion traps, where the heat bath can be simulated with the help of LASER light. In the limit of strong coupling a semiclassical description of the reduced quantum system is discussed. Again, an analytically exact expression for the entropy production and the corresponding fluctuation theorem is derived. A physical system, in which strong coupling to the environment can be analyzed, is given by Josephson junctions. This dissertation discusses the entropy production for isolated, weakly coupled, and overdamped quantum systems. For these physical regimes analytical relation are derived and experimental systems proposed, with which the predictions can be verified.
We present a systematic thermodynamic analysis of nonsecular GKLS master equations. When some energy transitions in the system are comparable with the dissipative rate, the secular approximation is not valid, and the positivity of the dynamics must be ensured via other approximations. The dynamics then presents features reminiscent from strong coupling to the environment: e.g. the equilibrium state with an environment at thermal equilibrium is not a Gibbs state of the local system Hamiltonian and the dynamics couples energy coherences and populations. Nonetheless, we build a unified, consistent thermodynamic framework for those dynamics. We focus on two approximations beyond the full secular approximation (the local and the more accurate geometric-arithmetic approximations), and then employ systematic perturbation theory on microscopic expressions for the first and second law of thermodynamics which relate irreversibility to the increase of system-environment correlations. We show that, in spite of the weak system-bath coupling, the system-bath interaction energy participates to the energy balance, and is directly linked to the Lamb-shift Hamiltonian. We compare this microscopic entropy production with the definition based on the contractivity of the reduced system dynamics (Spohn inequality). We show that, unlike for secular master equations, the two entropy production rates differ because of the presence of non-vanishing stationary coherences in the energy eigenbasis. However, in the case of a single thermal bath, the difference is purely transient, and no work can be cyclically extracted from the steady-state despite its non-Gibbs form. Finally, we illustrate our results with simple examples, clarifying and completing the thermodynamic picture of Markovian dynamics in the quantum regime.
Abstract The quantum thermodynamics of the ideal gas is treated by means of the particle entropies σ=ka. The non-dimensional entropy numbers a are calculated by the extended, temperature-dependent Schrödinger equation applying periodic boundary conditions. The Boltzmann constant k represents the atomic entropy unit. The quantized particle entropies a are used to calculate the Boltzmann distribution f=exp(α−a), the density of entropy levels D(a), the dimensionless chemical potential α=μ/kT, etc. – The thermodynamics of the ideal gas is treated on the basis of entropy quanta by means of the density matrix formalism. In this way we obtain the total particle entropy A, the thermodynamic entropy S (equation of Sackur-Tetrode), the internal and the Helmholtz free energy E and F, respectively, etc. Moreover, it can also be shown on the basis of entropy quanta that the entropy of a closed system in thermal equilibrium has a maximum value, S=S max. Against this, the entropy S ′ of an arbitrary non-equilibrium state is always smaller, S′ < S max (second law of thermodynamics). – Application of ordinary density matrix theory to a closed system of N particles leads to the result that the entropy S does not change in time, dS/dt=0, regardless whether we consider an equilibrium state, S=S max, or a non-equilibrium state, S=S′. Consequently, S cannot irreversibly change from S′ to S max. However, any irreversible process is accompanied by a positive entropy production P=dS/dt>0. In order to overcome this obvious contradiction, we discuss the entropy evolution in time by means of the commutator equation G =i[ P , t ], which is deduced from very general assumptions. Here P and t are the operators of the entropy production P and the time t. Accordingly, P and t do not commute in general, and hence P and t are not sharply defined simultaneously. Instead we have uncertainties ΔP and Δt, which are expressed by the uncertainty relation of the N-particle system, ΔPΔt≥(1/2)|〈 G 〉|=(γ/2)k. This P − t uncertainty relation easily allows a discussion of the evolution of the entropy S in time t from S′ to S max. Now the irreversible steps are correctly described by the entropy production P=dS/dt > 0, and the thermal equilibrium by P=0, ∆P=0, and thus the lifetime ∆t=∞.
Abstract The quantum measurement problem arises from the coexistence of unitary Schr¨odinger evolution with the apparent nonunitary collapse of quantum states during observation. Despite extensive theoretical development, no consensus has been reached on a microscopic physical mechanism for state reduction within standard quantum theory. In this work, we present a complete dynamical theory of quantum measurement in which wavefunction collapse emerges from irreversible information transfer and entropy production in realistic system–detector–environment interactions. Starting from microscopic Hamiltonian models, we derive a stochastic nonlinear evolution equation for conditioned quantum states without introducing additional axioms or phenomenological parameters. We demonstrate that the effective collapse rate is uniquely determined by environmental entropy production and remains well-defined in thermal, non-Markovian, chaotic, and zero-temperature regimes. Using stochastic calculus and martingale theory, we establish the dynamical emergence of the Born probability rule and prove almost-sure convergence of measurement trajectories to definite outcomes. The theory exhibits robust many-body amplification, universal behavior in nonlinear detectors, and mathematical well-posedness in both finite- and infinite-dimensional settings. Compatibility with algebraic quantum field theory, renormalization theory, and stochastic semiclassical gravity is established, ensuring consistency with relativistic and high-energy physics. Extensive numerical simulations confirm analytical predictions, and a comprehensive experimental program is proposed, together with rigorous validation and replication protocols. Logical analysis demonstrates compatibility with Bell nonlocality, resolution of Wigner’s friend and Frauchiger–Renner paradoxes, and compliance with information-theoretic constraints. These results provide a unified physical explanation of quantum measurement as an emergent nonequilibrium process governed by universal thermodynamic and informational principles, integrating state reduction into the standard dynamical framework of physics.