Generalized Master Equation Research Articles

Compact and complete description of non-Markovian dynamics.

Generalized master equations provide a theoretically rigorous framework to capture the dynamics of processes ranging from energy harvesting in plants and photovoltaic devices to qubit decoherence in quantum technologies and even protein folding. At their center is the concept of memory. The explicit time-nonlocal description of memory is both protracted and elaborate. When physical intuition is at a premium, one would desire a more compact, yet complete, description. Here, we demonstrate how and when the time-convolutionless formalism constitutes such a description. In particular, by focusing on the dissipative dynamics of the spin-boson and Frenkel exciton models, we show how to: easily construct the time-local generator from reference reduced dynamics, elucidate the dependence of its existence on the system parameters and the choice of reduced observables, identify the physical origin of its apparent divergences, and offer analysis tools to diagnose their severity and circumvent their deleterious effects. We demonstrate that, when applicable, the time-local approach requires as little information as the more commonly used time-nonlocal scheme, with the important advantages of providing a more compact description, greater algorithmic simplicity, and physical interpretability. We conclude by introducing the discrete-time analog and a straightforward protocol to employ it in cases where the reference dynamics have limited resolution. The insights we present here offer the potential for extending the reach of dynamical methods, reducing both their cost and conceptual complexity.

Waiting time distributions of the electron transport in a quantum dot coupled to a Majorana bound state

We investigate theoretically the waiting time distribution (WTD) of the sub-gap electron transport through a quantum dot which is coupled to two normal metal leads and one Majorana bound state of a topological superconductor. Using the generalized master equation approach, we calculate and present the analytical expressions of the WTDs. It is found that the WTD is an even function of the energy level of the dot. For comparison, we also consider the case that the quantum dot is side coupled to an ordinary fermionic state. For an ordinary fermionic state, the WTD indicates quite different behavior when tuning the dot energy level with opposite signs. Moreover, we discuss the information contained in the g ( 2 ) function to investigate the bunching and antibunching of electron tunneling processes. • The WTD of the dot-MBS system is an even function of the energy level of the dot. • Quantum coherence induces an oscillatory g ( 2 ) function, and electron emission from the dot is antibunched. • Two successive waiting times are negatively correlated, and it is consistent with the antibunched electron emission.

Entanglement dynamics: Generalized master equation for uniformly accelerated two-level systems

We propose an alternative form for the quantum master equation in the theory of open quantum systems. This alternative formalism allows one to describe the dynamics of two-level systems moving along different hyperbolic trajectories with distinct proper times. In the Born-Markov approximation, we consider a quantum massless scalar field coupled with two-level systems. Starting from a separable state, we show the emergence of entanglement harvesting. For different proper accelerations we also verify the entanglement sudden death.

Master equation approach to magnon relaxation and dephasing

There has been a recent upsurge of interest in the quantum properties of magnons for quantum information processing. An important issue is to examine the stability of quantum states of magnons against various relaxation and dephasing channels. Since the interaction of magnons in magnetic systems may fall in the ultrastrong and even deep-strong coupling regimes, the relaxation process of magnon states is quite different from the more common quantum optical systems. Here we study the relaxation and dephasing of magnons based on the Lindblad formalism and derive a generalized master equation that describes the quantum dynamics of magnons. Employing this master equation, we identify two distinct dissipation channels for squeezed magnons, i.e., the local dissipation and collective dissipation, which play a role for both ferromagnets and antiferromagnets. The local dissipation is caused by the independent exchange of angular momentum between the magnonic system and the environment, while the collective dissipation is dressed by the parametric interactions of magnons and it enhances the quantumness and thermal stability of squeezed magnons. Further, we show how this formalism can be applied to study the pure dephasing of magnons caused by four-magnon scattering and magnon-phonon interactions. Our results provide the theoretical tools to study the decoherence of magnons within a full quantum-mechanical framework and further benefit the use of quantum states of magnons for information processing.

Homogeneous generalized master equation for an arbitrary initial state of a many-particle classical system

A special projection operator is introduced, which exactly transforms the Nakajima–Zwanzig inhomogeneous Generalized Master Equation (GME) with an irrelevant initial condition term (a source) into a completely closed homogeneous GME (with no initial correlations term) for the relevant part of an N-particle distribution function FN(t) for an arbitrary initial distribution function FN(0) of a system of classical particles. It resolves the problem of the derivation of a closed linear evolution equation from the Liouville equation with no “molecular chaos” type approximation. The obtained equation is equivalent to the completely closed equation for s-particle (s≤N) distribution function Fs(t). The initial correlations are accounted for in this equation in the modified by the introduced projection operator kernel governing the evolution of Fs(t). This equation is further simplified by presenting its kernel in the linear in the particles’ density n approximation. In this approximation the equations for one-particle F1(t) and two-particle F2(t) distribution functions are derived. Special attention is given to analyzing the equation for F1(t) and showed that this equation in the Markov approximation can be written as the linear Boltzmann or Landau (for a small interparticle interaction) equations but with additional terms caused by initial correlations.

Time-dependent projection operator and nonlinear generalized master equations.

By introducing a special time-dependent projection operator P(t), the nonlinear version of the Nakajima-Zwanzig inhomogeneous generalized master equation(GME) for the relevant part of the N-particle distribution function containing the irrelevant initial correlation term is derived. For this projection operator the relevant part of the N-particle distribution function is a product of the distribution function of a group of s (s≤N) selected particles F_{s}(t) and the distribution function F_{N-s}(t) of N-s particles constituting the "environment" for a group of s selected particles. Thus, the linear projection operator approach results in the exact nonlinear GME for the relevant part of the distribution function, which is equivalent to the exact nonlinear GME for the distribution function of the complex of s particles of interest. This equationis further specified in the first approximation in the particle density, and then considered for one-particle and two-particle distribution functions. Given that there is no satisfactory way of dealing with the initial correlation term, the approach is suggested to rigorously include this term into consideration by converting the obtained inhomogeneous GME into homogeneous form containing initial correlations in the kernel governing the evolution of the relevant part of the distribution function. The homogeneous nonlinear GME for a one-particle distribution function is considered and the conditions for its equivalence to the nonlinear Boltzmann equationare discussed.

Field-theoretical approach to open quantum systems and the Lindblad equation

We develop a systematic field-theoretical approach to open quantum systems based on condensed-matter many-body methods. The time evolution of the reduced density matrix for the open quantum system is determined by a transmission matrix. Developing diagrammatic perturbation theory, invoking Wick's theorem in connection with a Caldeira-Leggett quantum oscillator environment in thermal equilibrium, the transmission matrix satisfies a Dyson equation characterized by an irreducible kernel. Unlike the Nakajima-Zwanzig and standard approaches, the Dyson equation is equivalent to a general non-Markovian master equation for the reduced density matrix, incorporating secular effects and independent of the initial preparation. The kernel is determined by a systematic diagrammatic expansion in powers of the interaction. We consider the Born approximation for the kernel. Applying a condensed-matter pole or, equivalently, a quasiparticle-type approximation, equivalent to the usual assumption of a timescale separation, we derive a master equation of the Markov type. Furthermore, imposing the rotating-wave approximation, we obtain a Markov master equation of the Lindblad form. To illustrate the method, we consider the standard example of a single qubit coupled to a thermal heat bath.

Quantum trajectory framework for general time-local master equations

Master equations are one of the main avenues to study open quantum systems. When the master equation is of the Lindblad–Gorini–Kossakowski–Sudarshan form, its solution can be “unraveled in quantum trajectories” i.e., represented as an average over the realizations of a Markov process in the Hilbert space of the system. Quantum trajectories of this type are both an element of quantum measurement theory as well as a numerical tool for systems in large Hilbert spaces. We prove that general time-local and trace-preserving master equations also admit an unraveling in terms of a Markov process in the Hilbert space of the system. The crucial ingredient is to weigh averages by a probability pseudo-measure which we call the “influence martingale”. The influence martingale satisfies a 1d stochastic differential equation enslaved to the ones governing the quantum trajectories. We thus extend the existing theory without increasing the computational complexity.

Effect of vibrational modes on electron transfer directionality: Photosynthetic reaction centers.

It is shown in the example of the photosynthetic reaction centers (RCs) that the electron transfer can be directed by vibrational modes into the needed site where it is localized. In the case of the RC, it is the low vibrational mode that produces such an effect. We find that the electron transfer unidirectionality in the photosynthetic reaction center can be determined by the asymmetry in the reorganization energy of the vibrational modes at high temperatures. We also numerically solve generalized master equationsfor various vibration relaxation times. The results are compared with the solution of master equations. It is shown that for small relaxation times, the non-Markovian electron transfer kinetics gives similar results as the Markovian approximation, but the results are significantly different for the long vibration relaxation times.

Precession of entangled spin and pseudospin in double quantum dots

Quantum dot spin valves are characterized by exchange fields which induce spin precession and generate current spin resonances even in absence of spin splitting. Analogous effects have been studied in double quantum dots, in which the orbital degree of freedom, the pseudospin, replaces the spin in the valve configuration. We generalize, now, this setup to allow for arbitrary spin and orbital polarization of the leads, thus obtaining an even richer variety of current resonances, stemming from the precession dynamics of entangled spin and pseudospin. We observe for both vectors a delicate interplay of decoherence, pumping and precession which can only be understood by also considering the dynamics of the spin-pseudospin correlators. The numerical results are obtained in the framework of a generalized master equation within the cotunneling approximation and are complemented by the analytics of a coherent sequential tunneling model.

Generalized master equation for charge transport in a molecular junction: Exact memory kernels and their high order expansion.

We derive a set of generalized master equations (GMEs) to study charge transport dynamics in molecular junctions using the Nakajima-Zwanzig-Mori projection operator approach. In the new GME, time derivatives of population on each quantum state of the molecule, as well as the tunneling current, are calculated as the convolution of time non-local memory kernels with populations on all system states. The non-Markovian memory kernels are obtained by combining the hierarchical equations of motion (HEOM) method and a previous derived Dyson relation for the exact kernel. A perturbative expansion of these memory kernels is then calculated using the extended HEOM developed in our previous work [M. Xu et al., J. Chem. Phys. 146, 064102 (2017)]. By using the resonant level model and the Anderson impurity model, we study properties of the exact memory kernels and analyze convergence properties of their perturbative expansions with respect to the system-bath coupling strength and the electron-electron repulsive energy. It is found that exact memory kernels calculated from HEOM exhibit short memory times and decay faster than the population and current dynamics. The high order perturbation expansion of the memory kernels can give converged results in certain parameter regimes. The Padé and Landau-Zener resummation schemes are also found to give improved results over low order perturbation theory.

Feynman-Vernon influence functional approach to quantum transport in interacting nanojunctions: An analytical hierarchical study

We present a nonperturbative and formally exact approach for the charge transport in interacting nanojunctions based on a real-time path-integral formulation of the reduced system dynamics. For reservoirs of noninteracting fermions, the exact trace over the leads' degrees of freedom results in the time-nonlocal Feynman-Vernon influence functional, a functional of the Grassmann-valued paths of the nanojunction, which induces correlations among the tunneling transitions in and out of the nanojunction. An expansion of the influence functional in terms of the number of tunneling transitions, and integration of the Grassmann variables between the tunneling times, allows us to obtain a still exact generalized master equation for the populations of the reduced density matrix in the occupation-number representation, as well as a formally exact expression for the current. By borrowing the nomenclature of the famous spin-boson model, we parametrize the two-state dynamics of each single-particle fermionic degree of freedom, in the occupation-number representation, in terms of blips and sojourns. We apply our formalism to the exactly solvable resonant level model (RLM) and to the single-impurity Anderson model (SIAM), the latter being a prototype system for studying strong correlations. For both systems, we demonstrate a hierarchical diagrammatic structure. While the hierarchy closes at the second tier for the RLM, this is not the case for the interacting SIAM. Upon inspection of the current kernel, known results from various perturbative and nonperturbative approximation schemes to quantum transport in the SIAM are recovered. Finally, a noncrossing approximation for the hierarchical kernel is developed, which enables us to systematically decrease temperature at each next level of the approximation. Analytical results for a simplified fourth-tier scheme are presented both in equilibrium and nonequilibrium and with an applied magnetic field.

Effects of symmetry breaking of the structurally-disordered Hamiltonian ensembles on the anisotropic decoherence of qubits

It is commonly known that the dephasing in open quantum systems is due to the establishment of bipartite correlations with ambient environments, which are typically difficult to be fully characterized. Recently, a new approach of average over disordered Hamiltonian ensemble is developed and shown to be capable of describing the nonclassicality of incoherent dynamics based on inferring the nonclassical nature of the correlations. Here we further extend the approach of Hamiltonian ensemble in the canonical form to the realm of structural disorder. Under the variable separation of the probability distribution within the Hamiltonian ensemble, the geometrical structure is easily visualized and can be characterized according to the degree of symmetry. We demonstrate four degrees and investigate the effects of different types of symmetry breaking on the incoherent dynamics. We show that these effects are easily understood from the emergences of additional terms in the master equations, leading to rather general master equations and, consequently, going beyond the previous frameworks of pure dephasing or isotropic depolarization.

Two-photon-interaction effects in the bad-cavity limit

Taking advantage of recently developed adiabatic elimination techniques, the authors investigate two-photon light-matter interactions in a system comprised of an oscillator and a collection of qubits operating in the ``bad-cavity'' regime. They derive a general master equation which unveils some unexpected effects of two-photon couplings, like a richer dependence on temperature of the collective quantum phenomena with respect to the one-photon-coupling case.

Effect of radiation physics on inherent statistics of glow curves from small samples or low doses

A theory is developed to predict statistical noise in the trap populations of small samples or single grains subjected to high-energy ionizing irradiation. Using a model of the radiation process and a one-trap one-center model of a thermoluminescent (TL) material, the statistical behavior of the number of occupied traps during irradiation is predicted. The model focuses on the inherent physics of the process. Experimental sources of error are not considered. The interaction of radiation with the TL material is modeled in a simple way using the Bethe equation. The trap and center populations in the TL material are modeled both with the conventional phenomenological equations and also the more general Master Equation approach. The theory predicts, as the irradiation process proceeds, the mean, standard deviation, dispersion, skewness, and kurtosis of the probability distribution of occupied traps in the TL material. For the same applied dose, the standard deviation and dispersion of the trap population depend strongly on the type of radiation as well as the shape and orientation of the material. High-energy radiation sources, such as alpha, beta, or gamma rays, are found to produce standard deviations and dispersion much larger than low-energy sources, such as UV radiation. The results are summarized in tables which enable, for useful limiting cases, easy calculation of not just standard deviation but also skewness and kurtosis for various radiation sources and geometries.

Homogeneous Generalized Master Equation for an Arbitrary Initial State of a Many-Particle Classical System

Homogeneous Generalized Master Equation for an Arbitrary Initial State of a Many-Particle Classical System

The time-fractional kinetic equation for the non-equilibrium processes

In this study, we consider the non-Markovian dynamics of the generic non-equilibrium kinetic process. We summarize the generalized master equation, the continuous and discrete forms of the time-fractional diffusion equation. Using path integral formulation, we generalized the solutions of the Markovian system to the non-Markovian for the non-equilibrium kinetic processes. Then, we obtain the time-fractional kinetic equation for the non-equilibrium systems in terms of free energy. Finally, we introduce a time-fractional equation to analyse time evolution of the open probability for the deformed voltage-gated ion-channel system as an example.

Nonuniqueness of generalized quantum master equations for a single observable

When deriving exact generalized master equations for the evolution of a reduced set of degrees of freedom, one is free to choose what quantities are relevant by specifying projection operators. However, obtaining a reduced description does not always need to be achieved through projections-one can also use conservation laws for this purpose. Such an operation should be considered as distinct from any kind of projection; that is, projection onto a single observable yields a different form of master equation compared to that resulting from a projection followed by the application of a constraint. We give a simple example to show this pointand give relationships that the different memory kernels must satisfy to yield the same dynamics.

Master equation incorporating the system-environment correlations present in the joint equilibrium state

We present a general master equation, correct to second order in the system-environment coupling strength, that takes into account the initial system-environment correlations. We assume that the system and its environment are in a joint thermal equilibrium state, and thereafter a unitary operation is performed to prepare the desired initial system state, with the system Hamiltonian possibly changing thereafter as well. We show that the effect of the initial correlations shows up in the second-order master equation as an additional term, similar in form to the usual second-order term describing relaxation and decoherence in quantum systems. We apply this master equation to a generalization of the paradigmatic spin-boson model, namely a collection of two-level systems interacting with a common environment of harmonic oscillators, as well as a collection of two-level systems interacting with a common spin environment. We demonstrate that, in general, the initial system-environment correlations need to be accounted for in order to accurately obtain the system dynamics.

Markov State Models to Study the Functional Dynamics of Proteins in the Wake of Machine Learning.

Markov state models (MSMs) based on molecular dynamics (MD) simulations are routinely employed to study protein folding, however, their application to functional conformational changes of biomolecules is still limited. In the past few years, the field of computational chemistry has experienced a surge of advancements stemming from machine learning algorithms, and MSMs have not been left out. Unlike global processes, such as protein folding, the application of MSMs to functional conformational changes is challenging because they mostly consist of localized structural transitions. Therefore, it is critical to properly select a subset of structural features that can describe the slowest dynamics of these functional conformational changes. To address this challenge, we recommend several automatic feature selection methods such as Spectral-OASIS. To identify states in MSMs, the chosen features can be subject to dimensionality reduction methods such as TICA or deep learning based VAMPNets to project MD conformations onto a few collective variables for subsequent clustering. Another challenge for the application of MSMs to the study of functional conformational changes is the ability to comprehend their biophysical mechanisms, as MSMs built for these processes often require a large number of states. We recommend the recently developed quasi-MSMs (qMSMs) to address this issue. Compared to MSMs, qMSMs encode the non-Markovian dynamics via the generalized master equation and can significantly reduce the number of states. As a result, qMSMs can be built with a handful of states to facilitate the interpretation of functional conformational changes. In the wake of machine learning, we believe that the rapid advancement in the MSM methodology will lead to their wider application in studying functional conformational changes of biomolecules.