Abstract Some basic concepts of the Prigogine quantum statistical theory of irreversible processes are discussed in connection with a previous paper by Chatzidimitriou‐Dreismann and Lippert. The removal of the “dual role” that the Hamiltonian plays within conventional quantum theory corresponds to the introduction of a star‐unitary operator 𝒯 called “intrinsic time.” The formalism of the previous paper is extended to systems that interact with external fields. A formal specification of 𝒯, furthermore, follows from the Lt invariance of the basic equations of motion and its connection with the intrinsic time. As an application to fluorescence spectroscopy, a photon counting experiment is presented. It allows us to detect certain predicted “dynamical” fluctuations in emission spectra. Some current experimental results are reported concerning the resolution of the broad fluorescence band of fluoranthene (dissolved in ethanol) through detection of the underlying finer vibrational structure.
Abstract Some basic concepts of the Prigogine quantum statistical theory of irreversible processes are discussed in connection with a previous paper by Chatzidimitriou‐Dreismann and Lippert. The removal of the “dual role” that the Hamiltonian plays within conventional quantum theory corresponds to the introduction of a star‐unitary operator 𝒯 called “intrinsic time.” The formalism of the previous paper is extended to systems that interact with external fields. A formal specification of 𝒯, furthermore, follows from the Lt invariance of the basic equations of motion and its connection with the intrinsic time. As an application to fluorescence spectroscopy, a photon counting experiment is presented. It allows us to detect certain predicted “dynamical” fluctuations in emission spectra. Some current experimental results are reported concerning the resolution of the broad fluorescence band of fluoranthene (dissolved in ethanol) through detection of the underlying finer vibrational structure.
Abstract Prigogine has emphasized that there is a “degeneracy” in quantum theory, where the Hamiltonian plays a dual role as (a) the generator of time evolution and (b) the energy observable. This prevents the exact treatment of irreversible phenomena on the microscopic quantum mechanical level. The removal of the aforementioned degeneracy can be achieved with the aid of a star‐unitary similarity transformation depending explicitly on the star‐Hermitian operator of the “intrinsic time”. Its physical significance is shown in the context of luminescence spectroscopy, where a novel kind of (dynamically induced or D‐) fluctuations around steady photoemission states is predicted. A photon counting/spectroscopic experiment has been performed which permits to detect D‐fluctuations and, at the same time, allows us to resolve broad spectroscopic bands by detection of the underlying finer “pure” vibronic transitions. The experimental findings clearly show the physical significance of Prigogine's Microscopic Theory.
Some basic concepts of the Prigogine microscopic theory of irreversibility are discussed in the physical context of molecular dynamical processes in condensed systems. The removal of the “dual role” that the Hamiltonian plays within conventional quantum theory corresponds to the introduction of a star-Hermitian superoperator called “intrinsic time.” The existence of dynamically induced fluctuations around steady states is predicted. With the aid of a new photon-counting experiment these fluctuations have been detected. The experiment allows us to resolve broad luminescence bands through the detection of the underlying vibrational structure.
Intrinsic theory of irreversibility In connection with the previous chapter on Wigner–Weisskopf, quantum irreversibility, Gamov states and the Lax–Phillips theory of decay, we shall examine the recent program in statistical mechanics carried forward by Ilya Prigogine and his colleagues since his early book in 1962 (Prigogine, 1962). This discussion is somewhat out of the focus of the present book, since the work to be discussed has principally been devoted to isolated quantum systems, not those in interaction with “reservoirs.” In addition, Prigogine's work is very classical in its content. We shall not attempt the task of reviewing the many changes that have taken place between 1962 and the present. Fine texts describing some of this work are those of Balescu (1963, 1975). A recent critical overview of the “modern view” is in the unpublished thesis of B. C. Bishop of the University of Texas Philosophy Department (Bishop, 1999). In many ways this is related to the use of Gel'fand triplets (Gel'fand and Vilenkin, 1968), mentioned in Chapter 17.6, to describe irreversible quantum states, i.e. Gamov states. See Chapter 17, the book of Bohm and Gadella (1989) and also the more recent review article by Bohm and colleagues (Bohm et al. , 1997). The object in statistical mechanics is to extend the range of the Liouville operator (classical and quantum) such that its eigenvalues are complex and intrinsically irreversible. Statistical mechanics has always been focused on many particle systems and the appearance of a continuum spectrum in the thermodynamic limit, already used in many places in this book. In the classical case Antoniou and Tasaki carried out the adaptation of the Gel'fand triplet approach to the Liouville operator, but this is, apparently, not possible quantum mechanically (Antoniou and Tasaki, 1993). Thus, another route must be taken in what Prigogine has termed, for emphasis, “large Poincaré systems” which have a continuum spectrum (Prigogine, 1997).
In many problems of molecular physics of condensed matter the coupling V of the system of interest with its environment is strong. During a time interval of the order of the characteristic relaxation time ΓTy due to V, both the energy spectrum and the time evolution of the system cannot be determined exactly. A new representation is introduced in which the coupling V does not affect the energy spectrum, but it determines the time evolution. This causes the appearance of a new quantity ΓT, called “intrinsic time.” Some results of this procedure are (a) invariance of the basic physical equations under the new trnsformation, (b) noncommutation of ΓT with the Liouvillian, and (c) existence of a nonvanishing “entropy production” with respect to the intrinsic time.
It is difficult to incorporate the concept of interacting physical particles in the frame of conventional quantum mechanics. It comes from the fact that in this formalism the Hamiltonian plays a dual role as the generator of motion and as the observable associated with the energy. As a result it is easy to define either a representation in which particles interact but are not well defined (a representation in which the Hamiltonian is not diagonal) or a representation in which the units are well defined but do not interact. We expect that in the search for a representation in which we may speak of both well defined and still interacting particles, the distinction between reversible and irreversible processes should play a basic role. Certainly we do not want to eliminate irreversible processes such as scattering, production or decay which are basically related to the mechanisms through which we observe particles. To distinguish between reversible and irreversible processes we have to work in a representation such that a Liapounov function (the entropy) may be ascribed to the time evolution of the system. The introduction of such a representation through a specific class of non-unitary transforms is described. We then propose newmore » quantum rules directly applicable to dissipative systems with a Liapounov function. For systems with a discrete spectrum these new quantum rules reduce trivially to the usual quantum rules as formulated by Born, Jordan and Heisenberg. The theory is applied to a simple field theoretical model - the so-called Friedrichs model-for which all calculations can be performed exactly.« less
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.