Dynamic master equation

We remark that the simulation scheme for master equation dynamics has a number of attractive features when compared to quantum-classical Liouville dynamics. The solution of the master equation consists of two numerically simple parts. The first is the computation of the memory function which involves adiabatic evolution along mean surfaces. Once the transition rates are known as a function of the subsystem coordinates, the sequential short-time propagation algorithm may be used to evolve the observable or density. Since the dynamics is restricted to single adiabatic surfaces, no phase factors... 

R. Grunwald and R. Kapral. Decoherence and quantum-classical master equation dynamics. J. Chem. Phys., 126(11) 114109, 2007. 

Evans DA, Wales DJ, Dian BC, Zwier TS (2004) The dynamics of conformational isomerization in flexible biomolecules. II. Simulating isomerizations in a supersonic free jet with master equation dynamics. J Chem Phys 120 148... 

C3.3.5.1 MASTER EQUATION ANALYSIS OF UNIMOLECULAR REACTION DYNAMICS... 

Here t. is the intrinsic lifetime of tire excitation residing on molecule (i.e. tire fluorescence lifetime one would observe for tire isolated molecule), is tire pairwise energy transfer rate and F. is tire rate of excitation of tire molecule by the external source (tire photon flux multiplied by tire absorjDtion cross section). The master equation system (C3.4.4) allows one to calculate tire complete dynamics of energy migration between all molecules in an ensemble, but tire computation can become quite complicated if tire number of molecules is large. Moreover, it is commonly tire case that tire ensemble contains molecules of two, tliree or more spectral types, and experimentally it is practically impossible to distinguish tire contributions of individual molecules from each spectral pool. 

Master equation methods are not tire only option for calculating tire kinetics of energy transfer and analytic approaches in general have certain drawbacks in not reflecting, for example, certain statistical aspects of coupled systems. Alternative approaches to tire calculation of energy migration dynamics in molecular ensembles are Monte Carlo calculations [18,19 and 20] and probability matrix iteration [21, 22], amongst otliers. 

Do we expect this model to be accurate for a dynamics dictated by Tsallis statistics A jump diffusion process that randomly samples the equilibrium canonical Tsallis distribution has been shown to lead to anomalous diffusion and Levy flights in the 5/3 < q < 3 regime. [3] Due to the delocalized nature of the equilibrium distributions, we might find that the microstates of our master equation are not well defined. Even at low temperatures, it may be difficult to identify distinct microstates of the system. The same delocalization can lead to large transition probabilities for states that are not adjacent ill configuration space. This would be a violation of the assumptions of the transition state theory - that once the system crosses the transition state from the reactant microstate it will be deactivated and equilibrated in the product state. Concerted transitions between spatially far-separated states may be common. This would lead to a highly connected master equation where each state is connected to a significant fraction of all other microstates of the system. [9, 10]... 

Immediately when the dynamic interpretation of Monte Carlo sampling in terms of the master equation, Eq. (31), was realized an application to study the critical divergence of the relaxation time in the two-dimensional Ising nearest-neighbor ferromagnet was attempted . For kinetic Ising and Potts models without any conservation laws, the consideration of dynamic universality classespredicts where z is the dynamic exponent , but the... 

The transition probabilities W% C C) cannot be arbitrary but must guarantee that the equilibrium state P C) is a stationary solution of the master equation (5). The simplest way to impose such a condition is to model the microscopic dynamics as ergodic and reversible for a fixed value of X ... 

The parameter is the damping constant, and (n) is the mean number of reservoir photons. The quantum theory of damping assumes that the reservoir spectrum is flat, so the mean number of reservoir oscillators (n) = ( (O)bj(O j) = ( (1 / ) — 1) 1 in the yth mode is independent of j. Thus the reservoir oscillators form a thermal system. The case ( ) = 0 corresponds to vacuum fluctuations (zero-temperature heat bath). It is convenient to consider the quantum dynamics of the system (56)-(59) in the interaction picture. Then the master equation for the density operator p is given by... 

The magnitude of the off-diagonal Hamiltonian (i.e. the energy transfer rate) thus depends on the strengths of the electron-phonon and Coulombic couplings and also the overlap of the two exciton wavefunctions[53]. Energy transfer rates from states to state jx, are calculated via the golden rule [54] and used as inputs to a master equation calculation of the excitation transfer kinetics in PSI, in which the dynamical information is included in the matrix K. 

In this paper we present a brief discussion and comparison of the probabilistic and dynamic approaches to the treatment of nonequilibrium phenomena in physical systems. The discussion is not intended to be complete but only illustrative. Details of many of the derivations appear elsewhere and only the results will be discussed here. We shall focus our attention on the probabilistic approach and shall emphasize its advantages and drawbacks. The main body of the paper deals with the properties of the master equation and, more cursorily, with the properties of the Langevin equation. 

Equation (5.1) described the vibrational response of a single particle to an applied forceF(t). In a (crystalline) system of many mobile particles (ensemble), the problem is analogous but the question now is how the whole system responds to an external force or perturbation Let us define the system s state (a) as a particular configuration of its particles and the probability of this state as pa. In a thermodynamic system, transitions from an a to a p configuration occur as thermally activated events. If the transition frequency a- /5 is copa and depends only on a and / (Markovian), the time evolution of the system is given by a master equation which links atomic and macroscopic parameters (dynamics and kinetics)... 

The dynamics associated with the Hamiltonian Eq. (8) or its variants Eq. (11) and Eq. (14) can be treated at different levels, ranging from the explicit quantum dynamics to non-Markovian master equations and kinetic equations. In the present context, we will focus on the first aspect - an explicit quantum dynamical treatment - which is especially suited for the earliest, ultrafast events at the polymer heterojunction. Here, the coherent vibronic coupling dynamics dominates over thermally activated events. On longer time scales, the latter aspect becomes important, and kinetic approaches could be more appropriate. 

Time-Local Quantum Master Equations and their Applications to Dissipative Dynamics and Molecular Wires... 

In Fig. 3, the simulation results for the same model problem are presented using the QCLE, the master equation, Tully s surface-hopping approach, the mean field approach, and adiabatic dynamics. The algorithmic details of each approach can be found elsewhere [2,40,79]. 

Fig. 3 Forward rate coefficient kAB(t) as a function of time for f3 = 1.0. The upper (blue) curve is the adiabatic rate, the purple curve is the result obtained by Tully s surface-hopping algorithm, the middle (black) curve is the quantum master equation result, the green curve is the QCL result, and the lowest dashed line (grey) is the result using mean-field dynamics.

From Eq. (3.34), one can obtain the generalized master equation (GME), which describes the dynamics of populations and coherences (or phases) of the systems. 

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