We show that the projection operators P usually employed to derive the Nakajima–Zwanzig master equation are non-Hermitian. As a consequence the operator QLQ which governs the dynamics of subsystem-reservoir interactions (here Q=1−P and L is the Liouville operator) is also non-Hermitian and possesses a complex temperature-dependent spectrum of resonances. We use the self-consistent Born approximation to derive a formula for the spectral density of QLQ. From this spectral density we calculate the memory function and mean relaxation time of subsystem-reservoir correlations. These formulas are compared with numerical results obtained from the spin–spin-bath model to test their accuracy. The memory function and mean relaxation time are essential ingredients for the SRA (statistical resonance approximation) theory of microscopic dissipation and decoherence. We show that the SRA master equation preserves positivity when the memory function derived in this paper is employed.
We show that the projection operators P usually employed to derive the Nakajima–Zwanzig master equation are non-Hermitian. As a consequence the operator QLQ which governs the dynamics of subsystem-reservoir interactions (here Q=1−P and L is the Liouville operator) is also non-Hermitian and possesses a complex temperature-dependent spectrum of resonances. We use the self-consistent Born approximation to derive a formula for the spectral density of QLQ. From this spectral density we calculate the memory function and mean relaxation time of subsystem-reservoir correlations. These formulas are compared with numerical results obtained from the spin–spin-bath model to test their accuracy. The memory function and mean relaxation time are essential ingredients for the SRA (statistical resonance approximation) theory of microscopic dissipation and decoherence. We show that the SRA master equation preserves positivity when the memory function derived in this paper is employed.
A non-Markovian master equation is derived for the reduced probability density matrix of a subsystem interacting with a general reservoir of coupled anharmonic modes. Relaxation of the subsystem is mediated through resonant interactions with the reservoir. These interactions correspond to local vibrational motions with finite lifetimes due to diffusion/dephasing. The derivation assumes that the density of these interaction modes is very large so that they can be treated using statistical methods. The resulting master equation is shown to preserve probability, Hermiticity, and translational invariance, and conditions are stated which guarantee the positivity of the reduced density. At long time the master equation reduces to a Markovian equation of dynamical semigroup type. In the high temperature limit the theory is parameter free, and shows good agreement with the exact master equation of a spin-boson system.
This preprint presents a self-contained and mathematically explicit reconstruction of the Gorini-Kossakowski-Sudarshan-Lindblad (GKSL) master equation starting from exact microscopic unitary dynamics through the Nakajima-Zwanzig projection operator formalism. Beginning with the exact non-local generalized master equation, we systematically analyze the hierarchy of approximations required for the emergence of a Markovian quantum dynamical semigroup. The Born (weak-coupling), Markov (time-localization), and secular approximations are derived and interpreted as successive information-reduction steps, each associated with clearly identifiable mathematical assumptions and physical consequences. Particular attention is devoted to the role of secularization in transforming the Redfield generator into a completely positive GKSL structure. To provide a concrete worked example, the formalism is applied to a damped two-level system coupled to a bosonic thermal reservoir, where the Redfield and GKSL equations are derived explicitly and compared at the microscopic level. Beyond the derivation itself, the work develops a systematic map of validity limits and failure regimes. The breakdown of the Born, Markov, secular, factorization, and stationarity assumptions is analyzed in terms of environmental correlation times, spectral-density structure, non-Markovian memory effects, information backflow, and loss of semigroup behavior. The resulting framework clarifies the precise operational domain in which GKSL dynamics can be regarded as a physically reliable effective description and provides a rigorous foundation for applications involving entropy-production theorems, quantum thermodynamics, and open-system information theory.
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.
Abstract This chapter introduces the density operator and the Liouville equation and outlines how reduced dynamical description of open quantum systems naturally leads to the appearance of relaxation processes. (1) The density operator and the quantum Liouville equation (the density matrix for a pure system, statistical mixtures, representations, coherences, thermodynamic equilibrium). (2) An example: The time evolution of a two-level system in the density matrix formalism. (3) Reduced descriptions. (4) Time evolution equations for reduced density operators: The quantum master equation (projection operators, The Nakajima–Zwanzig equation, Derivation of the quantum master equation using the thermal projector, The quantum master equation in the interaction representation, The Markovian limit—the Redfield equation, The secular approximation and the Lindblad equation). (5) The Lindblad equation in the ‘Heisenberg representation’. (6) Relaxation of a two-level system and a harmonic oscillator revisited. (7) The optically driven two-level system in a thermal environment—the Bloch equations. (8) The oscillating dipole model of a two-level molecule. (9) Analogy of a coupled two-level system to a spin ½ system in a magnetic field.
The conditions under which quantum-classical Liouville dynamics may be reduced to a master equation are investigated. Systems that can be partitioned into a quantum-classical subsystem interacting with a classical bath are considered. Starting with an exact non-Markovian equation for the diagonal elements of the density matrix, an evolution equation for the subsystem density matrix is derived. One contribution to this equation contains the bath average of a memory kernel that accounts for all coherences in the system. It is shown to be a rapidly decaying function, motivating a Markovian approximation on this term in the evolution equation. The resulting subsystem density matrix equation is still non-Markovian due to the fact that bath degrees of freedom have been projected out of the dynamics. Provided the computation of nonequilibrium average values or correlation functions is considered, the non-Markovian character of this equation can be removed by lifting the equation into the full phase space of the system. This leads to a trajectory description of the dynamics where each fictitious trajectory accounts for decoherence due to the bath degrees of freedom. The results are illustrated by computations of the rate constant of a model nonadiabatic chemical reaction.