It is well known that the statistics of closed classical systems evolves according to the Liouville theorem. Here we study the dynamics of the marginal statistics of classical systems coupled to external degrees of freedom, by developing a time-local equation of motion using Green's functions and a series expansion method. We also compare this equation of motion with its supposed quantum counterpart, namely the quantum master equation, which we hope could shed some light on quantum-classical analogy (QCA) from the perspective of "open system dynamics". We notice an apparent exception to QCA in this case, as the first-order classical equation of motion derived herein contains a term that does not appear to have a quantum analogue. We also propose possible ways of getting around this tension, which may help re-establish QCA (in first perturbative order). We do not draw a definitive conclusion about QCA in the context of open system dynamics but hope to provide a starting point for investigations along this line.
It is well known that the statistics of closed classical systems evolves according to the Liouville theorem. Here we study the dynamics of the marginal statistics of classical systems coupled to external degrees of freedom, by developing a time-local equation of motion using Green's functions and a series expansion method. We also compare this equation of motion with its supposed quantum counterpart, namely the quantum master equation, which we hope could shed some light on quantum-classical analogy (QCA) from the perspective of "open system dynamics". We notice an apparent exception to QCA in this case, as the first-order classical equation of motion derived herein contains a term that does not appear to have a quantum analogue. We also propose possible ways of getting around this tension, which may help re-establish QCA (in first perturbative order). We do not draw a definitive conclusion about QCA in the context of open system dynamics but hope to provide a starting point for investigations along this line.
A theoretical framework for the nonequilibrium statistical mechanics of open systems is constructed. This is concerned with a formulation of a generalized master equation governing the evolution of an arbitrary system S in interaction with a ``large'' reservoir R. The dynamics of S are analyzed on the basis of a precise quantum-mechanical treatment of the microscopic equations of motion for the combined system S + R. On proceeding to the thermodynamical limit for R we obtain a generalized master equation for S, subject to specified conditions on the many-particle structure of R, its initial state, and its coupling to S. This master equation corresponds to a self-contained law of motion for S, in which the R variables appear only in the forms of certain thermal averages, taken over the initial state. This dynamical law is a generalization of the quantum-mechanical Liouville equation to a form appropriate to open systems.
In this thesis quantum-classical dynamics is applied to the study of quantum condensed phase processes. This approach is based on the quantum-classical Liouville equation where the dynamics of a small subset of the degrees of freedom are treated quantum mechanically while the remaining degrees of freedom are treated by classical mechanics to a good approximation. We use this approach as it is computationally tractable, and the resulting equation of motion accurately accounts for the quantum and classical dynamics, as well as the coupling between these two components of the system. \n\nBy recasting the quantum-classical Liouville equation into the form of a generalized master equation we investigate connections to surface-hopping. The link between these approaches is decoherence arising from interaction of the subsystem with the environment. We derive an evolution equation for the subsystem which contains terms accounting for the effects of the environment. One of these terms involves a memory kernel that accounts for the coherent dynamics. If this term decays rapidly, a Markovian approximation can be made. By lifting the resulting subsystem master equation into the full phase space, we obtain a Markovian master equation that prescribes surface-hopping-like dynamics. Our analysis outlines the conditions under which such a description is valid.\n\nNext, we consider the calculation of the rate constant for a quantum mechanical barrier crossing process. Starting from the reactive-flux autocorrelation function, we derive a quantum-classical expression for the rate kernel. This expression involves quantum-classical evolution of a species operator averaged over the initial quantum equilibrium structure of the system making it possible to compute the rate constant via computer simulation. Using a simple model for a proton transfer reaction we compare the results of the rate calculation obtained by quantum-classical Liouville dynamics with that of master equation dynamics. The master equation provides a good approximation to the full quantum-classical Liouville calculation for our model and a more stable algorithm results due to the elimination of oscillating phase factors in the simulation. \n\nFinally, we make use of the theoretical framework established in this thesis to analyze some aspects of decoherence used in popular surface-hopping techniques.
A classical statistical probability amplitude is introduced whose square modulus is the distribution function. This enables the analogy between classical statistical mechanics and quantum mechanics to be completed. The analogy is developed until quantum statistical derivations can be used in classical statistical mechanics. Two master equations are found: the classical equivalent of the Pauli Master Equation, and a generally valid master equation. Well-known classical equations are deduced from these in a special representation. Interference terms are found and discussed.
Open quantum systems have drawn attention over decades due to its applicability in the foundation of theoretical physics, e.g. statistical mechanics, quantum mechanics and condensed matter physics. The dynamics of open quantum systems has been described as separate entities from their surrounding environment that consists of a very large number of modes, somehow coupled to the mode of the system. Even though the exact solution of the dynamical behavior of the system is impossible to calculate, we obtain a tentative solution using the crucial Markov approximation. The input-output formalism of the quantum Langevin equation (QLE) has been considered as a useful tool which provides a semi-classical description of the dynamics of the system, whereas the master equation provides a complete picture of the dynamics of the system expressed in terms of density matrix. While studying the dynamics of nonlinear system/environment coupling using QLE, we see, for a small value of external field, that the steady state system field does not change much from the steady state field obtained in the absence of nonlinear dissipation. However, in a case where a stronger external field is applied, we see that the deviation becomes substantial from the solution of linear system. We also see that the nonlinear coupling introduces significant difference in the cavity fluctuation spectrum. The description, therefore, provides a potential explanation of parametric effects in terms of nonlinear dissipation phenomena associated with the nonlinear coupling. Even though the theories developed in the context of open quantum systems have proven to be powerful tools, they do not provide a satisfactory platform to be implemented on non-linear Hamiltonians. We often approximate it by linearizing over nonlinear steady state field amplitude, and therefore, the interesting effects are often overlooked. The limitation of the analytics provokes us to simulate open quantum dynamics numerically. The numerical method consists of transformation of the environmental degrees of freedom to a one-dimensional many-body chain, and the computational technique includes numerical diagonalization and renormalization process. The time-adaptive density matrix renormalisation group (t-DMRG) is known as one of the most powerful techniques for the simulation of strongly-correlated many-body quantum systems. In this thesis, along with the theoretical modeling, we implement DMRG numerical scheme for the simulation of canonical S/B model by mapping it to one-dimensional harmonic chain with nearest neighbor interactions, and use the method to investigate the dynamics of the free dissipative system. The thermalization of open quantum systems is also studied by generating minimally entangled typical thermal states (METTS) through imaginary time evolution, and real-time evolving an empty system in the presence of the thermal bath. Further, we simulate coherently driven free dissipative Kerr nonlinear system numerically using Euler's method by solving Heisenberg equation of motion and t-DMRG algorithm, and demonstrate how the numerical results are analogous to classical bistability. By comparing with analytics, we see that the DMRG numerics is analogous to the quantum-mechanical exact solution obtained by mapping the equation of motion of the density matrix of the system to a Fokker-Plank equation. The comparison between two different numerical techniques shows that the semi-classical Euler's method determines the dynamics of the system field of one among two coherent branches, whereas DMRG numerics gives the superposition of both of them. Hence, DMRG-determined time dynamics undergoes generating non-classical states. Our approach of dealing with nonlinearity represents an important contribution in the developments of technique to study the dynamical and steady-state behavior of open quantum systems, which is a fundamental aspect of quantum physics.
We explore some aspects of nonequilibrium statistical mechanics of classical and quantum systems. Two chapters are devoted to fluctuation theorems which were originally derived for classical systems. The main challenge in formulating them in quantum mechanics is the fact that fundamental quantities of interest, like work, are defined via the classical concept of a phase space trajectory. We utilize the decoherent histories conceptual framework, in which classical trajectories emerge in quantum mechanics as a result of coarse graining, and provide a first-principles analysis of the nonequilibrium work relation of Jarzynski and Crooks's fluctuation theorem for a quantum system interacting with a general environment based on the quantum Brownian motion (QBM) model. We indicate a parameter range at low temperatures where the theorems might fail in their original form. Fluctuation theorems of Jarzynski and Crooks for systems obeying classical Hamiltonian dynamics are derived under the assumption that the initial conditions are sampled from a canonical ensemble, even though the equilibrium state of an isolated system is typically associated with the microcanonical ensemble. We address this issue through an exact analysis of the classical Brownian motion model. We argue that a stronger form of ensemble equivalence than usually discussed in equilibrium statistical mechanics is required for these theorems to hold in the infinite environment limit irrespective of the ensemble used, and proceed to prove it for this model. An exact expression for the probability distribution of work is obtained for finite environments. Intuitively one expects a system to relax to an equilibrium state when brought into contact with a thermal environment. Yet it is important to have rigorous results that provide conditions for equilibration and characterize the equilibrium state. We consider the dynamics of open quantum systems using the Langevin and master equations and rigorously show that under fairly general conditions quantum systems interacting with a heat bath relax to the equilibrium state defined as the reduced thermal state of the system plus environment, even in the strong coupling regime. Our proof is valid to second-order in interaction strength for general systems and exact for the linear QBM model, for which we also show the equivalence of multi-time correlations. In the final chapter we give a sampling of our investigations into macroscopic quantum phenomena. We work out in detail a specific example of how and under what conditions the center of mass (CoM) coordinate of a macroscopic object emerges as the relevant degree of freedom. Interaction patterns are studied in terms of the couplings they induce between the CoM and relative coordinates of two macroscopic objects. We discuss the implications of these interaction patterns on macroscopic entanglement.
A formulation of quantum statistical ensembles in terms of probability distributions on a projective Hilbert space is developed. The combination of statistically independent systems and the reduction of a system to one of its subsystems are described by means of a tensor product of probability distributions and a reduction formula for the reduced probability distribution. Within this framework the dynamics of open quantum systems is investigated starting form a microscopic system-plus-reservoir model. Employing the Markov approximation of the classical theory of stochastic processes the short time behavior of the conditional transition probability is derived and shown to yield a differential Chapman-Kolmogorov equation. The latter has the form of a Liouville master equation for the reduced probability distribution of the open quantum system. Thus it is shown that the time-dependent wave function of an open quantum system represents a well-defined and unique stochastic process in the space of rays of the underlying Hilbert space. This stochastic process consists of a continuous time evolution generated by a nonlinear Schr\"odinger equation and a discontinuous jump process; the realizations of the processes correspond to those of the Monte Carlo wave function simulation method and to those of the jump-type evolution of the quantum trajectory method. The quantum master equation for the statistical operator is derived as the equation of motion for the two-point correlation function of the stochastic process.