Data of the numerical solution of the time-dependent Schrödinger equation of a system containing one spin-1/2 particle interacting with a bath of up to 32 spin-1/2 particles is used to construct a Markovian quantum master equation describing the dynamics of the system spin. The procedure of obtaining this quantum master equation, which takes the form of a Bloch equation with time-independent coefficients, accounts for all non-Markovian effects inasmuch the general structure of the quantum master equation allows. Our simulation results show that, with a few rather exotic exceptions, the Bloch-type equation with time-independent coefficients provides a simple and accurate description of the dynamics of a spin-1/2 particle in contact with a thermal bath. A calculation of the coefficients that appear in the Redfield master equation in the Markovian limit shows that this perturbatively derived equation quantitatively differs from the numerically estimated Markovian master equation, the results of which agree very well with the solution of the time-dependent Schrödinger equation.
Data of the numerical solution of the time-dependent Schrödinger equation of a system containing one spin-1/2 particle interacting with a bath of up to 32 spin-1/2 particles is used to construct a Markovian quantum master equation describing the dynamics of the system spin. The procedure of obtaining this quantum master equation, which takes the form of a Bloch equation with time-independent coefficients, accounts for all non-Markovian effects inasmuch the general structure of the quantum master equation allows. Our simulation results show that, with a few rather exotic exceptions, the Bloch-type equation with time-independent coefficients provides a simple and accurate description of the dynamics of a spin-1/2 particle in contact with a thermal bath. A calculation of the coefficients that appear in the Redfield master equation in the Markovian limit shows that this perturbatively derived equation quantitatively differs from the numerically estimated Markovian master equation, the results of which agree very well with the solution of the time-dependent Schrödinger equation.
It is shown that by fitting a Markovian quantum master equation to the numerical solution of the time-dependent Schrödinger equation of a system of two spin-1/2 particles interacting with a bath of up to 34 spin-1/2 particles, the former can describe the dynamics of the two-spin system rather well. The fitting procedure that yields this Markovian quantum master equation accounts for all non-Markovian effects in as much the general structure of this equation allows and yields a description that is incompatible with the Lindblad equation.
The theory of open quantum systems represents one of the major developments of quantum mechanics over the last 50 years. Its central object of study is constituted by quantum systems that cannot be regarded as fully isolated, but instead interact with additional degrees of freedom, giving rise to irreversible phenomena such as dissipation and decoherence. The tools provided by this framework are nowadays of paramount importance across many active areas of research, including quantum computation, thermodynamics, metrology and biology. In this thesis, we investigate three main topics within the field. The first contribution concerns the microscopic derivation of the evolution equations, socalled quantum master equations, for open systems which are also subject to external driving fields. Standard techniques developed for time-independent Hamiltonians encounter several difficulties in the time-dependent case, largely restricting their applicability to specific instances, such as periodic or adiabatic drivings. In contrast, a core result of the derivation presented in the thesis is that, when the environment is sufficiently Markovian (essentially, memoryless), the non-adiabatic contributions to the driving field can be neglected in a controlled fashion, yielding an accurate master equation with time-dependent generator, capable of correctly reproducing the open dynamics even for strong drivings. This result is further supported by benchmarks against numerically exact simulations. The second contribution addresses the long-time behavior of general types of (Markovian) quantum master equations, including those of the form introduced above. While this problem has been extensively analyzed in the time-independent setting, virtually no results are known for time-dependent generators. In particular, we establish the foundations of a general theory of relaxation, that is, convergence towards an asymptotic trajectory in the long-time limit, independently of the initial state. The main results include a theorem guaranteeing sufficient conditions for relaxation and the derivation of a rate function governing the convergence to the asymptotic trajectory. The analysis is further extended to a simple non-Markovian case. Moreover, we treat in detail the specific master equation derived in the first part, connecting the aforementioned relaxation property directly to the underlying microscopic dynamics. The third contribution investigates chirality-induced spin selectivity (CISS) effects from the perspective of open quantum systems. Although the majority of theoretical studies aiming to model CISS are based on a coherent description of the spin dynamics, such effects have been observed also for electrons subject to incoherent transport across molecular networks. In this regard, we provide a rigorous ab initio derivation of the microscopic Hamiltonian describing the electronic transport, incorporating electron spin effects and contributions stemming from the nuclear vibrations. Within this result, we critically revise a master equation approach aiming to explain the origin of CISS effects observed in photosynthetic complexes. Taken together, these contributions offer fresh insights and original results on the interplay between driving fields and dissipation, relaxation phenomena, and electronic spin transport in the presence of incoherent dynamics. More broadly, these results provide new theoretical tools with several potential applications in quantum technologies, from modeling of control pulses in noisy environments to quantum reservoir engineering, and contribute to a deeper understanding of the role of quantum effects in biological systems.
We develop a Markovian master equation in the Lindblad form that enables the efficient study of a wide range of open quantum many-body systems that would be inaccessible with existing methods. The validity of the master equation is based entirely on properties of the bath and the system-bath coupling, without any requirements on the level structure within the system itself. The master equation is derived using a Markov approximation that is distinct from that used in earlier approaches. We provide a rigorous bound for the error induced by this Markov approximation; the error is controlled by a dimensionless combination of intrinsic correlation and relaxation timescales of the bath. Our master equation is accurate on the same level of approximation as the Bloch-Redfield equation. In contrast to the Bloch-Redfield approach, our approach ensures preservation of the positivity of the density matrix. As a result, our method is robust, and can be solved efficiently using stochastic evolution of pure states (rather than density matrices). We discuss how our method can be applied to static or driven quantum many-body systems, and illustrate its power through numerical simulation of a spin chain that would be challenging to treat by existing methods.
The non-Markovian master equation for open quantum systems is obtained by generalization of the ordinary Zwanzig-Nakajima (ZN) projection technique. To this end, a coupled chain of equations for the reduced density matrices of the bath ϱB(t) and the system ϱS(t) are written down. A formal solution of the equation for ϱB(t), having been inserted in the equation for the reduced density matrix of the system, in the 2-nd approximation in interaction yields a very specific extra term in the generalized master equation. This term, being nonlinear in ϱS(t), is related to the intrinsic bath dynamics and vanishes in the Markovian limit. To verify the consistence and robustness of our approach, we applied the generalized ZN projection scheme to a simple dephasing model. It is shown that consideration of the lowest order in interaction is insufficient to describe time evolution of the system coherence adequately. We explain this fact by analyzing the exact and approximate forms of ϱB(t) and give some hints how to take the dynamic correlations (which originate from the spin-bath coupling) into account.
One longstanding difficult problem in quantum dissipative dynamics is to solve the spin-boson model in a non-Markovian regime where a tractable systematic master equation does not exist. The spin-boson model is particularly important due to its crucial applications in quantum noise control and manipulation as well as its central role in developing quantum theories of open systems. Here we solve this important model by developing a non-Markovian quantum Langevin approach. By projecting the quantum Langevin equation onto the coherent states of the bath, we can derive a set of non-Markovian quantum Bloch equations containing no explicit noise variables. This special feature offers a tremendous advantage over the existing stochastic Schr\"odinger equations in numerical simulations. The physical significance and generality of our approach are briefly discussed.
The reduced dynamics of an open quantum system obtained from an underlying microscopic Hamiltonian can in general only approximately be described by a time-local master equation. The quality of that approximation depends primarily on the coupling strength and the structure of the environment. Various such master equations have been proposed with different aims. Choosing the most suitable one for a specific system is not straightforward. By focusing on the accuracy of the reduced dynamics we provide a thorough assessment for a selection of methods (Redfield equation, quantum optical master equation, coarse-grained master equation, a related dynamical map approach, and a partial-secular approximation). We consider secondary, here, whether or not an approach guarantees positivity. We use two qubits coupled to a Lorentzian environment in a spin-boson-like fashion modeling a generic situation with various system and bath time scales. We see that, independent of the initial state, the simple Redfield equation with time-dependent coefficients is significantly more accurate than all other methods under consideration. We emphasize that positivity violation in the Redfield equation formalism becomes relevant only in a regime where any of the perturbative master equations considered here are rendered invalid anyway. This implies that the loss of positivity should in fact be welcomed as an important feature: it indicates the breakdown of the weak-coupling assumption. In addition we present the various approaches in a self-contained way and use the behavior of their errors to provide further insight into the range of validity of each method.