We investigate the difference between a quantum and classical bath within the Caldeira-Leggett model for dissipative quantum dynamics.It is well known that a Markovian equation of motion for the reduced dynamics can be derived by taking the classical approximation of the harmonic bath correlation function.However, such approximation is only valid at high temperatures, and it is necessary to include the non-Markovian effect of the quantum bath in more general cases.We show that the equation of motion derived for the classical bath can be extended to the exact quantum one, by simply adding a real stochastic process to take account of the difference between the quantum and classical bath correlation functions.Numerical examples in calculating electron and excitation energy transfer dynamics, as well as absorption spectra of molecular aggregates indicate that the proposed method is a valid approach to extend the existing theories to include the quantum effect of the harmonic bath.The possibility of applying a similar idea to account for the difference between zero and high temperature quantum dissipative dynamics is discussed.
We investigate the difference between a quantum and classical bath within the Caldeira-Leggett model for dissipative quantum dynamics.It is well known that a Markovian equation of motion for the reduced dynamics can be derived by taking the classical approximation of the harmonic bath correlation function.However, such approximation is only valid at high temperatures, and it is necessary to include the non-Markovian effect of the quantum bath in more general cases.We show that the equation of motion derived for the classical bath can be extended to the exact quantum one, by simply adding a real stochastic process to take account of the difference between the quantum and classical bath correlation functions.Numerical examples in calculating electron and excitation energy transfer dynamics, as well as absorption spectra of molecular aggregates indicate that the proposed method is a valid approach to extend the existing theories to include the quantum effect of the harmonic bath.The possibility of applying a similar idea to account for the difference between zero and high temperature quantum dissipative dynamics is discussed.
We generalize the classical theory of Brownian motion so as to reckon with non-Markovian effects on both Klein-Kramers and Smoluchowski equations. For a free particle and a harmonic oscillator, it is shown that such non-Markovian effects account for the differentiability of the Brownian trajectories as well as the breakdown of the energy equipartition of statistical mechanics at short times in some physical situations. This non-Markovian approach is also extended to look at anomalous diffusion. Next, we bring in the dynamical-quantization method for investigating open quantum systems, which does consist in quantizing the classical Brownian motion starting directly from our non-Markovian Klein-Kramers and Smoluchowski equations, without alluding to any model Hamiltonian. Accordingly, quantizing our non-Markovian Klein-Kramers in phase space gives rise to a non-Markovian quantum master equation in configuration space, whereas quantizing our non-Markovian Smoluchowski equation in configuration space leads to a non-Markovian quantum Smoluchowski equation in phase space. In addition, it is worth noticing that non-Markovian quantum Brownian motion takes place in presence of a generic environment (e.g. a non-thermal quantum fluid). As far as the special case of a heat bath comprising of quantum harmonic oscillators is concerned, a non-Markovian Caldeira-Leggett master equation and a thermal quantum Smoluchowski equation are derived and extended to bosonic and fermionic heat baths valid for all temperatures.
The reduced dynamics of a quantum system interacting with a linear heat bath finds an exact representation in terms of a stochastic Schrödinger equation. All memory effects of the reservoir are transformed into noise correlations and mean-field friction. The classical limit of the resulting stochastic dynamics is shown to be a generalized Langevin equation, and conventional quantum state diffusion is recovered in the Born-Markov approximation. The non-Markovian exact dynamics, valid at arbitrary temperature and damping strength, is exemplified by an application to the dissipative two-state system.
We establish that the exact quantum dynamics of a Brownian particle in the Caldeira-Leggett model, with at most quadratic external potential, can be mapped, at any temperature, onto a classical, non-Markovian stochastic process in phase space. Starting from a correlated thermal equilibrium state between the particle and bath, we demonstrate that this correspondence is exact for quadratic potentials under arbitrary quantum state preparations of the particle itself. Our approach allows to consider arbitrary initial quantum states - including highly non-classical superpositions - which are incorporated via their Wigner functions, which serve as statistical weights for trajectory ensembles. Furthermore, the formalism naturally accommodates external manipulations and measurements modeled by preparation functions acting at arbitrary times, enabling the simulation of complex driven-dissipative quantum protocols. For more general, smooth potentials, we identify a natural small parameter: the density matrix becomes strongly quasidiagonal in the coordinate representation, with its off-diagonal width shrinking as the bath's spectral cutoff increases, suggesting a controlled parameter for a possible approximation.
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.
The exact dynamics of a system coupled to an environment can be described by an integro-differential stochastic equation for the reduced density. The influence of the environment is incorporated through a mean field which is both stochastic and nonlocal in time and where the standard two-time correlation functions of the environment appear naturally. Since no approximation is made, the presented theory incorporates exactly dissipative and non-Markovian effects. Applications to the spin-boson model coupled to a heat bath with various coupling regimes and temperature show that the presented stochastic theory can be a valuable tool to simulate exactly the dynamics of open quantum systems. Links with the stochastic Schrödinger equation method and possible extensions to "imaginary time" propagation are discussed.
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.