We consider particle transport under the influence of time-varying driving forces, where fluctuation relations connect the statistics of pairs of time-reversed evolutions of physical observables. In many ``mesoscopic'' transport processes, the effective many-particle dynamics is dominantly classical while the microscopic rates governing particle motion are of quantum-mechanical origin. We here employ the stochastic path-integral approach as an optimal tool to probe the fluctuation statistics in such applications. Describing the classical limit of the Keldysh quantum nonequilibrium field theory, the stochastic path integral encapsulates the quantum origin of microscopic particle exchange rates. Dynamically, it is equivalent to a transport master equation which is a formalism general enough to describe many applications of practical interest. We apply the stochastic path integral to derive general functional fluctuation relations for current flow induced by time-varying forces. We show that the successive measurement processes implied by this setup do not put the derivation of quantum fluctuation relations in jeopardy. While in many cases the fluctuation relation for a full time-dependent current profile may contain excessive information, we formulate a number of reduced relations, and demonstrate their application to mesoscopic transport. Examples include the distribution of transmitted charge, where we show that the derivation of a fluctuation relation requires the combined monitoring of the statistics of charge and work.
We consider particle transport under the influence of time-varying driving forces, where fluctuation relations connect the statistics of pairs of time-reversed evolutions of physical observables. In many ``mesoscopic'' transport processes, the effective many-particle dynamics is dominantly classical while the microscopic rates governing particle motion are of quantum-mechanical origin. We here employ the stochastic path-integral approach as an optimal tool to probe the fluctuation statistics in such applications. Describing the classical limit of the Keldysh quantum nonequilibrium field theory, the stochastic path integral encapsulates the quantum origin of microscopic particle exchange rates. Dynamically, it is equivalent to a transport master equation which is a formalism general enough to describe many applications of practical interest. We apply the stochastic path integral to derive general functional fluctuation relations for current flow induced by time-varying forces. We show that the successive measurement processes implied by this setup do not put the derivation of quantum fluctuation relations in jeopardy. While in many cases the fluctuation relation for a full time-dependent current profile may contain excessive information, we formulate a number of reduced relations, and demonstrate their application to mesoscopic transport. Examples include the distribution of transmitted charge, where we show that the derivation of a fluctuation relation requires the combined monitoring of the statistics of charge and work.
An overview is given of recent advances in the nonequilibrium statistical mechanics of quantum systems and, especially, of time-reversal symmetry relations that have been discovered in this context. The systems considered are driven out of equilibrium by time-dependent forces or by coupling to large reservoirs of particles and energy. The symmetry relations are established for the exchange of energy and particles between the subsystem and its environment. These results have important consequences. In particular, generalizations of the Kubo formula and the Casimir-Onsager reciprocity relations can be deduced beyond linear response properties. Applications to electron quantum transport in mesoscopic semiconducting circuits are discussed.
The study of electrical currents in a regime where a description as a continuous flow fails and the particle nature becomes important, but where notions such as particle density or currents continue to be meaningful, will be at the heart of the present dissertation. Given such a mesoscopic system through which electrons flow, either actively through quantum pumping or passively due to a potential difference, we investigate quantities such as transferred charge, noise, current fluctuations, and relations between them. More generally we shall examine the statistics of particle transport. All discussions will concentrate on compact devices transferring charge between two one-dimensional reservoirs (the leads) of independent electrons. Firstly, we consider the generating function of the moments of transferred charge and we prove that it is given by the determinant of a single-particle operator. It is formally equivalent to a formula of Lesovik and Levitov, but is shown to be well-defined in the situations under consideration, whereas the former is not, in general. The mechanism leading to regularization is typical for mesoscopic systems: we consider a limiting case that reveals the fundamental structure of the problem. In fact, as suited for an open system, the leads contain an infinite number of charges. It follows mathematically that the second quantization ought to be carried out upon the Fermi sea and not upon the vacuum, a procedure known as the GNS construction. We shall rely heavily on operator algebraic techniques. The set of observables, the C*-algebra of canonical anticommutation relations, admits different representations for systems in the thermodynamic limit, which are described by their reduced one-particle density matrix. An important question will be the existence of operators such as the charge or the time evolution in a given representation, which induce so-called Bogoliubov transformations. These prerequisites at hand, we shall pose the problem of counting statistics clearly, prove that the regularized determinant emerges naturally, and show that it describes the transport of integer charges with non-negative probabilities. Secondly, we introduce a model of instantaneous scattering in which various examples can be computed explicitely. In particular, we show that the above theorem applies for scattering through a smoothly operating pump over a finite time interval. We also exhibit situations where the propagator does exist but the generating function is ambiguous. In a more computational approach, we then turn to the relation of individual moments of transferred charge to current correlators. It turns out that the former can indeed be expressed as integrals of the latter over time, provided the current operators are ordered according to Matthews’ T∗ ordering. It is given by first arranging the charge operators according to their time indices, and only then taking the time derivatives, which induce contact terms whose singular support lies along time coincidences. We shall give two derivations of this result, because the first one is transparent, and the second one is related to contradictory computations in the literature where the system is considered to be measured by an external spin. In the model of constant instantaneous scattering, we then argue from the Lesovik-Levitov determinant that the transport can be interpreted in terms of a binomial process in the long time limit. In a parallel computation, we concentrate on the third cumulant as defined by integration of current correlators and show how the contact terms of the T∗ ordering play an essential role in providing the expected binomial result, too. To close this thesis, we suggest an algebraic framework that lays the foundations for a rigorous discussion of the Casimir effect. The problem of infinites arising in the comparison of two physical situations for a bosonic field is interpreted as the non-equivalence of states on the algebra of canonical commutation relations. We exhibit sufficient conditions on the one-particle Hamiltonians which ensure that the Casimir energy is finite and give an expression for it. We discuss its formal equivalence with the result obtained from the standard mode summing method.
The thesis comprises two major themes of quantum statistical dynamics. One is the development of quantum dissipation theory (QDT). It covers the establishment of some basic relations of quantum statistical dynamics, the construction of several nonequivalent complete second-order formulations, and the development of exact QDT. Another is related to the applications of quantum statistical dynamics to a variety of research fields. In particular, unconventional but novel theories of the electron transfer in Debye solvents, quantum transport, and quantum measurement are developed on the basis of QDT formulations. The thesis is organized as follows. In Chapter 1, we present some background knowledge in relation to the afore-mentioned two themes of this thesis. The key quantity in QDT is the reduced density operator ρ(t) ≡ trBρT(t); i.e., the partial trace of the total system and bath composite ρT(t) over the bath degrees of freedom. QDT governs the evolu-tion of reduced density operator, where the effects of bath are treated in a quantum statistical manner. In principle, the reduced density operator contains all dynam-ics information of interest. However, the conventional quantum transport theory is formulated in terms of nonequilibrium Green's function. The newly emerging field of quantum measurement in relation to quantum information and quantum computing does exploit a sort of QDT formalism. Besides the background of the relevant theoretical development, some representative experiments on molecular nanojunctions are also briefly discussed. In Chapter 2, we outline some basic (including new) relations that highlight several important issues on QDT. The content includes the background of nonequi-librium quantum statistical mechanics, the general description of the total compos-ite Hamiltonian with stochastic system-bath interaction, a novel parameterization scheme for bath correlation functions, a newly developed exact theory of driven Brownian oscillator (DBO) systems, and its closely related solvation mode trans-formation of system-bath coupling Hamiltonian in general. The exact QDT of DBO systems is also used to clarify the validity of conventional QDT formulations that involve Markovian approximation. In Chapter 3, we develop three nonequivalent but all complete second-order QDT (CS-QDT) formulations. Two of them are of the conventional prescriptions in terms of time-local dissipation and memory kernel, respectively. The third one is called the correlated driving-dissipation equations of motion (CODDE). This novel CS-QDT combines the merits of the former two for its advantages in both the application and numerical implementation aspects. Also highlighted is the importance of correlated driving-dissipation effects on the dynamics of the reduced system. In Chapter 4, we construct an exact QDT formalism via the calculus on path integrals. The new theory aims at the efficient evaluation of non-Markovian dis-sipation beyond the weak system-bath interaction regime in the presence of time-dependent external field. By adopting exponential-like expansions for bath corre-lation function, hierarchical equations of motion formalism and continued fraction Liouville-space Green's function formalism are established. The latter will soon be used together with the Dyson equation technique for an efficient evaluation of non-perturbative reduced density matrix dynamics. The interplay between system-bath interaction strength, non-Markovian property, and the required level of hierarchy is also studied with the aid of simple spin-boson systems, together with the three proposed schemes to truncate the infinite hierarchy. In Chapter 5, we develop a nonperturbative theory of electron transfer (ET) in Debye solvents. The resulting exact and analytical rate expression is constructed on the basis of the aforementioned continued fraction Liouville-space Green's func-tion formalism, together with the Dyson equation technique. Not only does it re-cover the celebrated Marcus' inversion and Kramers' turnover behaviors, the new theory also shows some distinct quantum solvation effects that can alter the ET mechanism. Moreover, the present theory predicts further for the ET reaction ther-modynamics, such as equilibrium Gibbs free-energy and entropy, some interesting solvent-dependent features that are calling for experimental verification. In Chapter 6, we discuss the constructed QDTs, in terms of their unified math-ematical structure that supports a linear dynamics space, and thus facilitates their applications to various physical problems. The involving details are exemplified with the CODDE form of QDT. As the linear space is concerned, we identify the Schrödinger versus Heisenberg picture and the forward versus backward propaga-tion of the reduced, dissipative Liouville dynamics. For applications we discuss the reduced linear response theory and the optimal control problems, in which the correlated effects of non-Markovian dissipation and field driving are shown to be important. In Chapter 7, we turn to quantum transport, i.e. electric current through molecular or mesoscopic systems under finite applied voltage. By viewing the nonequilibrium transport setup as a quantum open system, we develop a reduced-density-matrix approach to quantum transport. The resulting current is explicitly expressed in terms of the molecular reduced density matrix by tracing out the degrees of freedom of the electrodes at finite bias and temperature. We propose a conditional quantum master equation theory, which is an extension of the conven-tional (or unconditional) QDT by tracing out the well-defined bath subsets indi-vidually, instead of the entire bath degrees of freedom. Both the current and the noise spectrum can be conveniently analyzed in terms of the conditional reduced density matrix dynamics. By far, the QDT (including the conditional one) has only been exploited in a second-order form. A self-consistent Born approximation for the system-electrode coupling is further proposed to recover all existing nonlinear current-voltage behaviors including the nonequilibrium Kondo effect. Transport theory based on the exact QDT formalism will be developed in future. In Chapter 8, we study the quantum measurement of a qubit with a quantum-point-contact detector. On the basis of a unified quantum master equation (a form of QDT), we study the measurement-induced relaxation and dephasing of the qubit . Our treatment pays particular attention on the detailed-balance relation, which is a consequence of properly accounting for the energy exchange between the qubit and detector during the measurement process. We also derive a conditional quantum master equation for quantum measurement in general, and study the readout characteristics of the qubit measurement. Our theory is applicable to the quantum measurement at arbitrary voltage and temperature. A number of remarkable new features are found and highlighted in concern with their possible relevance to future experiments. In Chapter 9, we discuss the further development of QDT, aiming at an effi-cient evaluation of many-electron systems. This will be carried out by reducing the many-particle (Fermion or Boson) QDT to a single-particle one by exploring, e.g. the Wick's contraction theorem. It also results in a time-dependent density func-tional theory (TDDFT) for transport through complex large-scale (e.g. molecules) systems. Primary results of the TDDFT-QDT are reported. In Chapter 10, we summary the thesis, and comment and remark on the future work on both the theoretical and application aspects of QDT.
Abstract The very notion of a current fluctuation is problematic in the quantum context. We study that problem in the context of nonequilibrium statistical mechanics, both in a microscopic setup and in a Markovian model. Our answer is based on a rigorous result that relates the weak coupling limit of fluctuations of reservoir observables under a global unitary evolution with the statistics of the so-called quantum trajectories. These quantum trajectories are frequently considered in the context of quantum optics, but they remain useful for more general nonequilibrium systems. In contrast with the approaches found in the literature, we do not assume that the system is continuously monitored. Instead, our starting point is a relatively realistic unitary dynamics of the full system
Abstract Processes at the nanoscale happen far away from the thermodynamic limit, far from equilibrium and are dominated by fluctuations and, perhaps, even quantum effects. This book establishes a consistent thermodynamic framework for such processes by combining tools from non-equilibrium statistical mechanics and the theory of open quantum systems. The book is accessible for graduate students and of interest to all researchers striving for a deeper understanding of the laws of thermodynamics beyond their traditional realm of applicability. It puts most emphasis on the microscopic derivation and understanding of key principles and concepts as well as their interrelation. The topics covered in this book include (quantum) stochastic processes, (quantum) master equations, local detailed balance, classical stochastic thermodynamics, (quantum) fluctuation theorems, strong coupling and non non-Markovian effects, thermodynamic uncertainty relations, operational approaches, Maxwell's demon and time-reversal symmetry, among other topics. Furthermore, the book treats a few applications in detail to illustrate the general theory and its potential for practical applications. These are single-molecule pulling experiments, quantum transport and thermoelectric effects in quantum dots, the micromaser and related set-ups in quantum optics.
Full understanding of the relaxation mechanisms and far-from-equilibrium transport in modern mesoscopic structures requires that such systems be treated as open. We therefore generalize some of the core elements of the Kadanoff-Baym-Keldysh nonequilibrium Green's function formalism, inherently formulated for closed systems, to treatment of an open system, coupled with its environment. We define the two-time correlation functions and analyze the influence of the memory effects on the open-system transport. In the transient regime, the two-time correlation functions clearly show four distinct terms: a closed-system-like term, an entanglement term, and two memory terms that depend explicitly on the initial state of the environment. We show that it is not possible to completely eliminate the influence of the environment by a fortunate choice of the initial state, and approximating the system as closed is valid only in the limit of negligible system-environment coupling, which is never the case in the transient regime. We derive the transport equations for transients that properly account for the system-environment coupling. On the other hand, we address the important issue of transport in a far-from-equilibrium steady state. We show that, once a steady state is reached, the balance between the driving and relaxation forces implies that the two-time correlation functions regain a closed-system-like form, but with an effective, modified system Hamiltonian, and with the system statistical operator unrelated to that of the initial state. We emphasize that the difference between the transient and the far-from-equilibrium steady-state regimes, crucial for theoretical investigation of nonequilibrium quasiparticle transport, effectively lies within the different relative magnitude of the combined entanglement and memory terms with respect to the closed-system-like term in two-time correlation functions.