The concept of complete positivity fixes in considerable detail the mathematical structure of quantum Markovian master equations which describe the combined reversible-irreversible dynamics of open systems for the case of time-independent Hamilton operators. For many applications such as, for instance, problems of time-resolved spectroscopy, similar results would be of great value but involve time-varying external fields with a corresponding time-dependent Hamiltonian. For this reason, we propose a suitable extension of the Kossakowski generator to the time-dependent case by maintaining complete positivity and using arguments suggested by experimental facts. As an example, generalized Bloch-like equations can be obtained with three different relaxation times and a nonlinear dependence upon field strength.
The concept of complete positivity fixes in considerable detail the mathematical structure of quantum Markovian master equations which describe the combined reversible-irreversible dynamics of open systems for the case of time-independent Hamilton operators. For many applications such as, for instance, problems of time-resolved spectroscopy, similar results would be of great value but involve time-varying external fields with a corresponding time-dependent Hamiltonian. For this reason, we propose a suitable extension of the Kossakowski generator to the time-dependent case by maintaining complete positivity and using arguments suggested by experimental facts. As an example, generalized Bloch-like equations can be obtained with three different relaxation times and a nonlinear dependence upon field strength.
The well-known magnetic or optical Bloch equations are extended to the case of unstable systems such as, e.g., spontaneously decaying particles and molecules undergoing chemical reactions or decaying from excited states back to states other than those involved in resonance. The modified equations are derived from a general theory of irreversible processes where quantum Markovian master equations and the corresponding completely positive dynamical semigroups dictate the time evolution of density operators. The results are of particular importance in those situations where decay occurs level-selectively and all relaxation and decay constants are of comparable order of magnitude. The obtained generalized Bloch equations are of direct applicability to problems of time-resolved magnetic or optical resonance spectroscopy.
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 study the concepts of complete positivity and positivity in a two-level open quantum system whose dynamics are governed by a time-local quantum master equation. We establish necessary and sufficient conditions on the time-dependent relaxation rates to ensure complete positivity and positivity of the dynamical map. We discuss their relations with the non-Markovian behavior of the open system. We also analyze the long-time asymptotic behavior of the dynamics as a function of the rates. We show under which conditions on the rates the system tends to an equilibrium state. Different examples illustrate this general study.
A well established approach to describe open quantum system dynamics is the celebrated Gorini-Kossakowski-Sudarshan-Lindblad (GKSL) master equation. In this article we aim to shed light on semigroup dynamics that are not of this form. Such dynamics may appear in real physical systems describing asymptotic long-time dynamics. Thus, they correspond to semigroup dynamics applicable to a restricted set of initial states only. As a way of motivating our studies, first we review known results about the single-mode Gaussian Quantum Brownian motion channel and corresponding master equations. Next we discuss a conceptually simpler family of qubit semigroup generators and identify parameter regions of completely positive, merely positive, and non-positive dynamics. We then focus on the latter case to which we will refer to as restricted-positive, as the semigroup generator may well be physically meaningful when applied to a restricted set of admissible initial states.
We investigate the long-time behavior of quantum Markovian dynamics generated by time-dependent Gorini–Kossakowski–Lindblad–Sudarshan (GKLS) master equations. We introduce a notion of weak relaxation and derive sufficient conditions guaranteeing asymptotic independence from the initial state. Our results provide a quantitative extension of the Spohn–Frigerio theorem to time-dependent generators, yielding explicit contraction bounds in terms of the instantaneous steady state and the jump operators. For a class of microscopically derived master equations, we further obtain a graph-theoretic characterization of the aforementioned conditions that directly links the structure of the jump operators to the relaxation properties. The general theory is illustrated by applications to driven finite-level systems, including a detailed three-level example, and is extended to a non-Markovian setting by means of time-local master equations that become of GKLS form at long times. These findings pave the way for the development of a more general theory of relaxation beyond the Markovian case.
To extend the classical concept of Markovianity to an open quantum system, different notions of the divisibility of its dynamics have been introduced. Here, we analyze this issue by five complementary approaches: equations of motion, real-time diagrammatics, Kraus-operator sums, as well as time-local and nonlocal (Nakajima-Zwanzig) quantum master equations. As a case study featuring several types of divisible dynamics, we examine in detail an exactly solvable noninteracting fermionic resonant level coupled arbitrarily strongly to a fermionic bath at an arbitrary temperature in the wideband limit. In particular, the impact of divisibility on the time-dependence of the observable level occupation is investigated and compared with typical Markovian approximations. We find that the loss of semigroup-divisibility is accompanied by a prominent reentrant behavior: Counter to intuition, the level occupation may temporarily increase significantly in order to reach a stationary state with smaller occupation, implying a reversal of the measurable transport current. In contrast, the loss of the so-called completely positive divisibility is more subtly signaled by the prohibition of such current reversals in specific time-intervals. Experimentally, it can be detected in the family of transient currents obtained by varying the initial occupation. To quantify the nonzero footprint left by the system in its effective environment, we determine the exact time-dependent state of the latter as well as related information measures such as entropy, exchange entropy, and coherent information.