Linear Master Equation Research Articles

Quantum Bernoulli noises approach to quantum master equations and applications to Ehrenfest-type theorems

This paper investigates the regularity properties of quantum master equations with unbounded coefficients within the space of square-integrable complex-valued Bernoulli functionals. Initially, we demonstrate the existence of a unique regular solution to the linear stochastic Schrödinger equation driven by cylindrical Brownian motions. Subsequently, we establish the existence of regular solutions for the autonomous linear quantum master equation and provide a probabilistic representation of this solution in terms of the stochastic Schrödinger equation. Finally, by taking the expectation of some observables with respect to the solution of the quantum master equation, we derive a system of differential equations that describe the evolution of the mean values of certain quantum observables.

Coherent control from quantum commitment probabilities.

We introduce a general definition of a quantum committor in order to clarify reaction mechanisms and facilitate control in processes where coherent effects are important. With a quantum committor, we generalize the notion of a transition state to quantum superpositions and quantify the effect of interference on the progress of the reaction. The formalism is applicable to any linear quantum master equation supporting metastability for which absorbing boundary conditions designating the reactant and product states can be applied. We use this formalism to determine the dependence of the quantum transition state on coherences in a polaritonic system and optimize the initialization state of a conical intersection model to control reactive outcomes, achieving yields of the desired state approaching 100%. In addition to providing a practical tool, the quantum committor provides a conceptual framework for understanding reactions in cases when classical intuitions fail.

Effective Hamiltonian approach to kinetic Ising models: Application to an infinitely long-range Husimi-Temperley model.

The probability distribution (PD) of spin configurations in kinetic Ising models has been cast in the form of the canonical Boltzmann PD with a time-dependent effective Hamiltonian (EH). It has been argued that in systems with extensive energy EH depends linearly on the number of spins N leading to the exponential dependence of PD on the system size. In macroscopic systems the argument of the exponential function may reach values of the order of the Avogadro number which is impossible to deal with computationally, thus making unusable the linear master equation (ME) governing the PD evolution. To overcome the difficulty, it has been suggested to use instead the nonlinear ME (NLME) for the EH density per spin. It has been shown that in spatially homogeneous systems NLME contains only terms of order unity even in the thermodynamic limit. The approach has been illustrated with the kinetic Husimi-Temperley model (HTM) evolving under the Glauber dynamics. At finite N the known numerical results has been reproduced and extended to broader parameter ranges. In the thermodynamic limit an exact nonlinear partial differential equationof the Hamilton-Jacobi type for EH has been derived. It has been shown that the average magnetization in HTM evolves according to the conventional kinetic mean field equation.

Initial correlations in open quantum systems: constructing linear dynamical maps and master equations

We investigate the dynamics of open quantum systems which are initially correlated with their environment. The strategy of our approach is to analyze how given, fixed initial correlations modify the evolution of the open system with respect to the corresponding uncorrelated dynamical behavior with the same fixed initial environmental state, described by a completely positive dynamical map. We show that, for any predetermined initial correlations, one can introduce a linear dynamical map on the space of operators of the open system which acts like the proper dynamical map on the set of physical states and represents its unique linear extension. Furthermore, we demonstrate that this construction leads to a linear, time-local quantum master equation with generalized Lindblad structure involving time-dependent, possibly negative transition rates. Thus, the general non-Markovian dynamics of an open quantum system can be described by means of a time-local master equation even in the case of arbitrary, fixed initial system–environment correlations. We present some illustrative examples and explain the relation of our approach to several other approaches proposed in the literature.

Information geometry, trade-off relations, and generalized Glansdorff–Prigogine criterion for stability

We discuss a relationship between information geometry and the Glansdorff–Prigogine criterion for stability. For the linear master equation, we found a relation between the line element and the excess entropy production rate. This relation leads to a new perspective of stability in a nonequilibrium steady-state. We also generalize the Glansdorff–Prigogine criterion for stability based on information geometry. Our information-geometric criterion for stability works well for the nonlinear master equation, where the Glansdorff–Prigogine criterion for stability does not work well. We derive a trade-off relation among the fluctuation of the observable, the mean change of the observable, and the intrinsic speed. We also derive a novel thermodynamic trade-off relation between the excess entropy production rate and the intrinsic speed. These trade-off relations provide a physical interpretation of our information-geometric criterion for stability. We illustrate our information-geometric criterion for stability by an autocatalytic reaction model, where dynamics are driven by a nonlinear master equation.

Derivation of the Redfield Quantum Master Equation and Corrections to It by the Bogoliubov Method

Following the ideas N. N. Bogoliubov used to derive the classical and quantum nonlinear kinetic equations, we derive the Redfield quantum linear master equation, which is widely used in the theory of open quantum systems. This method allows one to calculate the joint state of a system and a reservoir at every instant of time, as well as to obtain quantum master equations as autonomous differential equations in an arbitrary order of perturbation theory. We prove that under certain conditions the expressions for the corrections of all orders are well defined. We also discuss the question of whether the quantum dynamics described by the derived quantum master equations is Markovian.

Efficient and exact sampling of transition path ensembles on Markovian networks.

The problem of flickering trajectories in standard kinetic Monte Carlo (kMC) simulations prohibits sampling of the transition path ensembles (TPEs) on Markovian networks representing many slow dynamical processes of interest. In the present contribution, we overcome this problem using knowledge of the metastable macrostates, determined by an unsupervised community detection algorithm, to perform enhanced sampling kMC simulations. We implement two accelerated kMC methods to simulate the nonequilibrium stochastic dynamics on arbitrary Markovian networks, namely, weighted ensemble (WE) sampling and kinetic path sampling (kPS). WE-kMC utilizes resampling in pathway space to maintain an ensemble of representative trajectories covering the state space, and kPS utilizes graph transformation to simplify the description of an escape trajectory from a trapping energy basin. Both methods sample individual trajectories governed by the linear master equation with the correct statistical frequency. We demonstrate that they allow for efficient estimation of the time-dependent occupation probability distributions for the metastable macrostates, and of TPE statistics, such as committor functions and first passage time distributions. kPS is particularly attractive, since its efficiency is essentially independent of the degree of metastability, and we suggest how the algorithm could be coupled with other enhanced sampling methodologies. We illustrate our approach with results for a network representing the folding transition of a tryptophan zipper peptide, which exhibits a separation of characteristic timescales. We highlight some salient features of the dynamics, most notably, strong deviations from two-state behavior, and the existence of multiple competing mechanisms.

On the glass transition temperature Tg against molar volume Vm plotting in arsenoselenide glasses

Dependence of glass transition temperature Tg (K) on overall mean bonding energy E (kJ/mol) in arsenoselenide glass reexamined under per-atom calculations is shown to obey linearized master equation Tg ≅ 418⋅(E–1.13). Compositional variations in Tg against molar volume Vm are plotted for g-AsxSe100-x taken within (0 ≤ x ≤ 65) domain assuming preferential cohesive Van der Waals (VDW) bonding between network-constituting entities. The Tg values are found to vary as inverse-αth power of Vm, attaining distinct values for different networks, in part, 0D-molecular (α = =6/3 = 2), 1D-chained (α = =5/3), 2D-layered (α = =4/3), and 3D-spatial (α = =3/3 = 1). These variations originated from macroscopic geometry of VDW interaction are linearized in log-log presentation for networks dominated with chain-like 1D-entities (0 ≤ x<~8) and cross-linked 3D-entities (~8 < x< 30–33), while demonstrate non-linear behaviour for cross-linked 3D- and layered 2D-entities (30–33 < x < 40), and layered 2D- and molecular 0D-entities (40 < x < 65). Appearance of molecular entities in g-AsxSe100-x (40 < x < 65) results in self-terminated loop in log–log plotting of Tg(1/Vm) dependence.

Basic Properties of a Mean Field Laser Equation

We study the nonlinear quantum master equation describing a laser under the mean field approximation. The quantum system is formed by a single mode optical cavity and two level atoms, which interact with reservoirs. Namely, we establish the existence and uniqueness of the regular solution to the nonlinear operator equation under consideration, as well as we get a probabilistic representation for this solution in terms of a mean field stochastic Schrödinger equation. To this end, we find a regular solution for the nonautonomous linear quantum master equation in Gorini–Kossakowski–Sudarshan–Lindblad form, and we prove the uniqueness of the solution to the nonautonomous linear adjoint quantum master equation in Gorini–Kossakowski–Sudarshan–Lindblad form. Moreover, we obtain rigorously the Maxwell–Bloch equations from the mean field laser equation.

Perturbative Treatment for Stationary State of Local Master Equation**Supported by the National Natural Science Foundation of China under Grant Nos. 11675119, 11575125, and 11105097

The local approach to construct master equation for a composite open system with a weak internal coupling is simple and seems reasonable. However, it is thermodynamic consistent only when the subsystems are resonantly coupled. Efforts are being made to understand the inconsistency and test the validity of the local master equation. We present a perturbative method to solve the steady-state solutions of linear local master equations, which are demonstrated by two simple models. The solving process shows the stationary state as the result of competition between incoherent operations and the unitary creating quantum coherence, and consequently relate quantum coherence with thermodynamic consistency.

Entropic Distance for Nonlinear Master Equation

More and more works deal with statistical systems far from equilibrium, dominated by unidirectional stochastic processes, augmented by rare resets. We analyze the construction of the entropic distance measure appropriate for such dynamics. We demonstrate that a power-like nonlinearity in the state probability in the master equation naturally leads to the Tsallis (Havrda–Charvát, Aczél–Daróczy) q-entropy formula in the context of seeking for the maximal entropy state at stationarity. A few possible applications of a certain simple and linear master equation to phenomena studied in statistical physics are listed at the end.

Stochastic model of nanomechanical electron shuttles and symmetry breaking

Nanomechanical electron shuttles can work as ratchets for radio-frequency rectification. We develop a full stochastic model of coupled shuttles, where the mechanical motion of nanopillars and the incoherent electronic tunneling are modeled by a Markov chain. In particular, the interaction of their randomness is taken into account, so that a linear master equation is constructed. Numerical solutions from our fast approximate method and analytical derivation reveal the symmetry breaking, which results in the direct current observed in earlier measurements [Phys. Rev. Lett. 105, 067204 (2010)PRLTAO0031-900710.1103/PhysRevLett.105.067204]. Additionally, the method can facilitate device simulation of more complex designs such as shuttle arrays.

Biexponential decay and ultralong coherence of a qubit

A quantum two-state system, weakly coupled to a heat bath, is traditionally studied in the Born-Markov regime under the secular approximation with completely positive linear master equations. Despite its success, this microscopic approach exclusively predicts exponential decays and Lorentzian susceptibility profiles, in disagreement with a number of experimental findings. On the contrary, in the absence of the secular approximation they can be explained but with the risk of jeopardizing the positivity of the density matrix. To avoid these drawbacks, we use a physically motivated nonlinear master equation being both thermodynamically and statistically consistent. We find that, beyond a temperature-dependent threshold, a bifurcation in the decoherence time T2 takes place; it gives rise to a biexponential decay and a susceptibility profile being neither Gaussian nor Lorentzian. This implies that, for suitable initial states, a major prolongation of the coherence can be obtained in agreement with recent experiments. Moreover, T2 is no longer limited by the energy relaxation time T1 offering novel perspectives to elaborate devices for quantum information processing.

Asymptotic lower bound for the gap of Hermitian matrices having ergodic ground states and infinitesimal off-diagonal elements

Given a Hermitian matrix with possibly degenerate eigenvalues , we provide, in the limit M → ∞, a lower bound for the gap assuming that i) the eigenvector (eigenvectors) associated to is ergodic (are all ergodic) and ii) the off-diagonal terms of vanish for M → ∞. Under these hypotheses, we find . This general result turns out to be important for upper bounding the relaxation time of linear master equations characterized by a matrix equal, or isospectral, to . As an application, we consider symmetric random walks with infinitesimal jump rates and show that the relaxation time is upper bounded by the configurations (or nodes) with minimal degree.

The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation.

We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their "far from equilibrium behavior," hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative "external vector field" whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the "plasticity property" of biological systems and to their capabilities to switch from one state to another as is observed during synaptic plasticity, cell fate determination, and differentiation.

Eigenvalues of the homogeneous finite linear one step master equation: Applications to downhill folding

Motivated by the observed time scales in protein systems said to fold "downhill," we have studied the finite, linear master equation, with uniform rates forward and backward as a model of the downhill process. By solving for the system eigenvalues, we prove the claim that in situations where there is no free energy barrier a transition between single- and multi-exponential kinetics occurs at sufficient bias (towards the native state). Consequences for protein folding, especially the downhill folding scenario, are briefly discussed.

Initial-state preparation with dynamically generated system-environment correlations

The dependence of the dynamics of open quantum systems upon initial correlations between the system and environment is an utterly important yet poorly understood subject. For technical convenience most prior studies assume factorizable initial states where the system and its environments are uncorrelated, but these conditions are not very realistic and give rise to peculiar behaviors. One distinct feature is the rapid buildup or a sudden jolt of physical quantities immediately after the system is brought in contact with its environments. The ultimate cause of this is an initial imbalance between system-environment correlations and coupling. In this paper we demonstrate explicitly how to avoid these unphysical behaviors by proper adjustments of correlations and/or the coupling, for setups of both theoretical and experimental interest. We provide simple analytical results in terms of quantities that appear in linear (as opposed to affine) master equations derived for factorized initial states.

Quasi-steady State Reduction of Molecular Motor-Based Models of Directed Intermittent Search

We present a quasi-steady state reduction of a linear reaction-hyperbolic master equation describing the directed intermittent search for a hidden target by a motor-driven particle moving on a one-dimensional filament track. The particle is injected at one end of the track and randomly switches between stationary search phases and mobile nonsearch phases that are biased in the anterograde direction. There is a finite possibility that the particle fails to find the target due to an absorbing boundary at the other end of the track. Such a scenario is exemplified by the motor-driven transport of vesicular cargo to synaptic targets located on the axon or dendrites of a neuron. The reduced model is described by a scalar Fokker-Planck (FP) equation, which has an additional inhomogeneous decay term that takes into account absorption by the target. The FP equation is used to compute the probability of finding the hidden target (hitting probability) and the corresponding conditional mean first passage time (MFPT) in terms of the effective drift velocity V, diffusivity D, and target absorption rate λ of the random search. The quasi-steady state reduction determines V, D, and λ in terms of the various biophysical parameters of the underlying motor transport model. We first apply our analysis to a simple 3-state model and show that our quasi-steady state reduction yields results that are in excellent agreement with Monte Carlo simulations of the full system under physiologically reasonable conditions. We then consider a more complex multiple motor model of bidirectional transport, in which opposing motors compete in a "tug-of-war", and use this to explore how ATP concentration might regulate the delivery of cargo to synaptic targets.

The role of short-ranged energetic correlations in the mobility field dependence of disordered organic materials

We studied the mobility of charge carriers in a model for disordered organic solids where the energies of the localized states are Gaussianly distributed with short-ranged correlations. We obtained an expression for the mobility as a function of electric field, temperature, energetic variance, and correlation radius. The temperature dependence obtained with short-ranged energetic correlations is different from that obtained with power-law decaying energetic correlations and suggests a possible way to distinguish the two types of correlations from the measured mobility. This work also presents a practical way of computing the mobility, applicable to any transport model based on a linear master equation, directly from the matrix of the hopping rates.

Simplified Charge Separation Energetics in a Two-Dimensional Model for Polymer-Based Photovoltaic Cells

An extension of our two-dimensional working model for photovoltaic behavior in binary polymer and/or molecular photoactive blends is presented. The objective is to provide a more-realistic description of the charge generation and charge separation processes in the blend system. This is achieved by assigning an energy to each of the possible occupation states, describing the system according to a simple energy model for exciton and geminate electron-hole pair configurations. The energy model takes as primary input the ionization potential, electron affinity and optical gap of the components of the blend. The underlying photovoltaic model considers a nanoscopic subvolume of a photoactive blend and represents its p- and n-type domain morphology, in terms of a two-dimensional network of donor and acceptor sites. The nearest-neighbor hopping of charge carriers in the illuminated system is described in terms of transitions between different occupation states. The equations governing the dynamics of these states are cast into a linear master equation, which can be solved for arbitrary two-dimensional donor-acceptor networks, assuming stationary conditions. The implications of incorporating the energy model into the photovoltaic model are illustrated by simulations of the short circuit current versus thickness of the photoactive blend layer for different choices of energy parameters and donor-acceptor topology. The results suggest the existence of an optimal thickness of the photoactive film in bulk heterojunctions, based on kinetic considerations alone, and that this optimal thickness is very sensitive to the choice of energy parameters. The results also indicate space-charge limiting effects for interpenetrating donor-acceptor networks with characteristic domain sizes in the nanometer range and high driving force for the photoinduced electron transfer across the donor-acceptor internal interface.