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At least 37 records · Page 2Linked to original sources

Nonequilibrium theory of polymer stretching based on the master equation.

We present a model for fast polymer-stretching experiments. We use the master equation and argue that the end-to-end extension of a polymer molecule can be used as a stochastic variable after appropriate coarse graining. The main effect of increasing pulling speed or force loading rate is a marked hysteresis in the force-extension curve as well as an overall shift of the curve to higher forces when compared to the equilibrium curve. This can be understood in terms of the moments of the transition probability in the master equation. An analysis of the fluctuations and relaxation times is also given in the framework of our theory.

Journal Article↗

Uncoupled continuous-time random walks: Solution and limiting behavior of the master equation.

A detailed study is presented for a large class of uncoupled continuous-time random walks. The master equation is solved for the Mittag-Leffler survival probability. The properly scaled diffusive limit of the master equation is taken and its relation with the fractional diffusion equation is discussed. Finally, some common objections found in the literature are thoroughly reviewed.

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Nonequilibrium quantum dynamics in the condensed phase via the generalized quantum master equation.

The Nakajima-Zwanzig generalized quantum master equation provides a general, and formally exact, prescription for simulating the reduced dynamics of a quantum system coupled to a quantum bath. In this equation, the memory kernel accounts for the influence of the bath on the system's dynamics, and the inhomogeneous term accounts for initial system-bath correlations. In this paper, we propose a new approach for calculating the memory kernel and inhomogeneous term for arbitrary initial state and system-bath coupling. The memory kernel and inhomogeneous term are obtained by numerically solving a single inhomogeneous Volterra equation of the second kind for each. The new approach can accommodate a very wide range of projection operators, and requires projection-free two-time correlation functions as input. An application to the case of a two-state system with diagonal coupling to an arbitrary bath is described in detail. Finally, the utility and self-consistency of the formalism are demonstrated by an explicit calculation on a spin-boson model.

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Path summation formulation of the master equation.

Markovian dynamics, modeled by the kinetic master equation, has wide ranging applications in chemistry, physics, and biology. We derive an exact expression for the probability of a Markovian path in discrete state space for an arbitrary number of states and path length. The total probability of paths repeatedly visiting a set of states can be explicitly summed. The transition probability between states can be expressed as a sum over all possible paths connecting the states. The derived path probabilities satisfy the fluctuation theorem. The paths can be the starting point for a path space Monte Carlo procedure which can serve as an alternative algorithm to analyze pathways in a complex reaction network.

Computer Simulation↗

Determination of the temperature and pressure dependence of the reaction OH + C2H4 from 200-400 K using experimental and master equation analyses.

The pressure and temperature dependence for the reaction of OH + C(2)H(4) was studied over the range of conditions: 200-400 K and 5-600 Torr by laser flash photolysis, laser-induced fluorescence (FP-LIF). Additional experiments were conducted at room temperature by laser flash photolysis, cavity ring-down spectroscopy to facilitate determination of the high pressure limit. One-dimensional master equation calculations were conducted to test the temperature and pressure dependence of the reaction in He and in N(2). The energetics of the reaction and geometries of intermediate species were calculated by ab initio calculations (DFT-BH&HLYP/6-311+G(3df,2p) and CBS-APNO level along DFT-IRC, respectively. An investigation into the importance of a pre-reaction van der Waals complex on the kinetics over the pressure range of the troposphere is discussed. The high pressure rate coefficient was extracted by fitting the master equation calculations to the data and yields k(infinity) = 5.01 x 10(-12) exp(148/T) cm(3) molecule(-1) s(-1). The master equation calculations were then optimized for the pressure fall-off in He and N(2) by varying the average downward energy transfer parameter (DeltaE(down)) for the different collision partners and finally fitted to a Troe expression to determine k(o) and F(cent) for use in atmospheric modeling.

Ethylenes↗

The finite state projection algorithm for the solution of the chemical master equation.

This article introduces the finite state projection (FSP) method for use in the stochastic analysis of chemically reacting systems. One can describe the chemical populations of such systems with probability density vectors that evolve according to a set of linear ordinary differential equations known as the chemical master equation (CME). Unlike Monte Carlo methods such as the stochastic simulation algorithm (SSA) or tau leaping, the FSP directly solves or approximates the solution of the CME. If the CME describes a system that has a finite number of distinct population vectors, the FSP method provides an exact analytical solution. When an infinite or extremely large number of population variations is possible, the state space can be truncated, and the FSP method provides a certificate of accuracy for how closely the truncated space approximation matches the true solution. The proposed FSP algorithm systematically increases the projection space in order to meet prespecified tolerance in the total probability density error. For any system in which a sufficiently accurate FSP exists, the FSP algorithm is shown to converge in a finite number of steps. The FSP is utilized to solve two examples taken from the field of systems biology, and comparisons are made between the FSP, the SSA, and tau leaping algorithms. In both examples, the FSP outperforms the SSA in terms of accuracy as well as computational efficiency. Furthermore, due to very small molecular counts in these particular examples, the FSP also performs far more effectively than tau leaping methods.

Algorithms↗

Molecular-dynamics simulations and master-equation description of a chemical wave front: effects of density and size of reaction zone on propagation speed.

We compare the master-equation description and molecular-dynamics simulations of a chemical wave front. We find that the front propagation speed depends on the number of particles in the reaction zone. For the master equation the dependence follows the well-known logarithmic prediction obtained when introducing a cutoff into the macroscopic reaction-diffusion equation. The molecular-dynamics simulations reveal that the logarithmic law is compromised for dense fluids.

Journal Article↗

Efficient computation of the first passage time distribution of the generalized master equation by steady-state relaxation.

The generalized master equation or the equivalent continuous time random walk equations can be used to compute the macroscopic first passage time distribution (FPTD) of a complex stochastic system from short-term microscopic simulation data. The computation of the mean first passage time and additional low-order FPTD moments can be simplified by directly relating the FPTD moment generating function to the moments of the local FPTD matrix. This relationship can be physically interpreted in terms of steady-state relaxation, an extension of steady-state flow. Moreover, it is amenable to a statistical error analysis that can be used to significantly increase computational efficiency. The efficiency improvement can be extended to the FPTD itself by modelling it using a gamma distribution or rational function approximation to its Laplace transform.

Algorithms↗

Positivity preserving non-markovian master equations

A general class of integrodifferential non-Markovian master equations is developed which is representative of the dynamics of small subsystems interacting with open reservoirs with memory. Conditions which guarantee positivity of the subsystem reduced density are established.

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Master equation simulations of a model of a thermochemical system.

Master equation approach is used to study the influence of fluctuations on the dynamics of a model thermochemical system. For appropriate values of parameters, the deterministic description of the system gives the subcritical or supercritical Hopf bifurcations. For small systems (containing 100 000 particles) close to the supercritical Hopf bifurcation, the stochastic trajectories obtained from numerical simulations do not allow to distinguish between damped oscillations around a stable focus and sustained oscillations around a small stable limit cycle. This uncertainty disappears if the number of particles in the system is increased (up to 1 000 000). Close to subcritical Hopf bifurcation the stochastic trajectory of the system jumps from the basin of attraction of a stable focus to the basin of attraction of a stable limit cycle. In this case the time dependencies of temperature and concentration of reactant in the system are apparently similar to intermittent chaotic oscillations. The mean first passage time for the transitions from the stable focus to the stable limit cycle show the characteristic exponential dependence on the number of particles. This passage time depends very strongly on the bifurcation parameter (reaction heat), which determines the distance between the stable focus and an unstable limit cycle.

Journal Article↗

Time autocorrelation function analysis of master equation and its application to atomic clusters.

We derive the energy fluctuation Delta(2)E, and the time autocorrelation kappa(tau) and its Fourier transformation--the fluctuation spectra S(omega)--of the master-equation transition matrix. The contribution from each eigenmode of the transition matrix to these fluctuation quantities reveals the relevant importance of the individual mode in the relaxation processes. The time scales associated with these relaxation processes are determined by the corresponding eigenvalues. Unlike traditional time evolution analysis, the autocorrelation function and fluctuation spectra analysis does not involve an arbitrary initial population. It is also more suitable for analyzing the underlying dynamic, kinetic behavior near the equilibrium and the behavior of the long-time-scale rare events. We utilize our technique to analyze the solid-liquid phase coexistence of the 13-atom Morse cluster and the fcc-to-icosahedral structure transition of the 38-atom Lennard-Jones cluster. For the processes studied, the fluctuation spectra from the master equation simplify the analysis of the transition matrix, and the important relaxation modes are easily extracted.

Chemistry, Physical↗

Linear response to perturbation of nonexponential renewal process: A generalized master equation approach.

The work by Barbi, Bologna, and Grigolini [Phys. Rev. Lett. 95, 220601 (2005)] discusses a response to alternating external field of a non-Markovian two-state system, where the waiting time between the two attempted changes of state follows a power law. It introduced a new instrument for description of such situations based on a stochastic master equation with reset. In the present Brief Report we provide an alternative description of the situation within the framework of a generalized master equation. The results of our analytical approach are corroborated by direct numerical simulations of the system.

Journal Article↗

Exact quantum master equation via the calculus on path integrals.

An exact quantum master equation formalism is constructed for the efficient evaluation of quantum non-Markovian dissipation beyond the weak system-bath interaction regime in the presence of time-dependent external field. A novel truncation scheme is further proposed and compared with other approaches to close the resulting hierarchically coupled equations of motion. The interplay between system-bath interaction strength, non-Markovian property, and required level of hierarchy is also demonstrated with the aid of simple spin-boson systems.

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Master equation for retrodiction of quantum communication signals.

We derive the master equation that governs the evolution of the measured state backwards in time in an open system. This allows us to determine probabilities for a given set of preparation events from the results of subsequent measurements, which has particular relevance to quantum communication.

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Damped harmonic oscillator: pure states of the bath and exact master equations.

Time evolution of a harmonic oscillator linearly coupled to a heat bath is compared for three classes of initial states for the bath modes-grand canonical ensemble, number states, and coherent states. It is shown that for a wide class of number states the behavior of the oscillator is similar to the case of the equilibrium bath. If the bath modes are initially in coherent states, then the variances of the oscillator coordinate and momentum, as well as its entanglement to the bath, asymptotically approach the same values as for the oscillator at zero temperature and the average coordinate and momentum show a Brownian-like behavior. We derive an exact master equation for the characteristic function of the oscillator valid for arbitrary factorized initial conditions. In the case of the equilibrium bath this equation reduces to an equation of the Hu-Paz-Zhang type, while for the coherent states bath it leads to an exact stochastic master equation with a multiplicative noise.

Journal Article↗

The non-Markovian quantum master equation in the collective-mode representation: application to barrier crossing in the intermediate friction regime.

The calculation of chemical reaction rates in the condensed phase is a central preoccupation of theoretical chemistry. At low temperatures, quantum-mechanical effects can be significant and even dominant; yet quantum calculations of rate constants are extremely challenging, requiring theories and methods capable of describing quantum evolution in the presence of dissipation. In this paper we present a new approach based on the use of a non-Markovian quantum master equation (NM-QME). As opposed to other approximate quantum methods, the quantum dynamics of the system coordinate is treated exactly; hence there is no loss of accuracy at low temperatures. However, because of the perturbative nature of the NM-QME it breaks down for dimensionless frictions larger than about 0.1. We show that by augmenting the system coordinate with a collective mode of the bath, the regime of validity of the non-Markovian master equation can be extended significantly, up to dimensionless frictions of 0.5 over the entire temperature range. In the energy representation, the scaling goes as the number of levels in the relevant energy range to the third power. This scaling is not prohibitive even for chemical systems with many levels; hence we believe that the current method will find a useful place alongside the existing techniques for calculating quantum condensed-phase rate constants.

Journal Article↗

Time-convolutionless master equation for mesoscopic electron-phonon systems.

The time-convolutionless master equation for the electronic populations is derived for a generic electron-phonon Hamiltonian. The equation can be used in the regimes where the golden rule approach is not applicable. The equation is applied to study the electronic relaxation in several models with the finite number of normal modes. For such mesoscopic systems the relaxation behavior differs substantially from the simple exponential relaxation. In particular, the equation shows the appearance of the recurrence phenomena on a time scale determined by the slowest mode of the system. The formal results are quite general and can be used for a wide range of physical systems. Numerical results are presented for a two level system coupled to Ohmic and super-Ohmic baths, as well as for a model of charge-transfer dynamics between semiconducting organic polymers.

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Numerical method for integrodifferential generalized Langevin and master equations.

We show that the integrodifferential generalized Langevin and non-Markovian master equations can be transformed into larger sets of ordinary-differential equations. On the basis of this transformation we develop a numerical method for solving such integrodifferential equations. Physically motivated example calculations are performed to demonstrate the accuracy and convergence of the method.

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