Coupled-master equations

This section briefly introduces the generalized coupled master equation within the Born-Oppenheimer adiabatic (BOA) approximation. In this case, the non-adiabatic processes are treated as the vibronic transitions between the vibronic manifolds. Three types of the rate constant are then introduced to specify the nature of the transitions depending on whether the electronically excited molecular system achieves its vibrational thermal equilibrium or not. The radiationless transitions can occur between two... 

Now pump-probe stimulated emission spectra can be determined on the basis of Eqs. (142)-(144). For this purpose, the coupled master equations are numerically solved and then using Eq. (128) pump-probe stimulated emission spectra are computed. For numerical simulation, the Runge-Kutta algorithm with a time step of 4 fsec is employed, and from 7 to 16... 

Martin s group has also performed the same type of measurements to wild-type RCs of Rh. sphaeroides [77], A rapid ET takes place upon an excitation of the special pair in this system. Since the bandwidth of the pumping pulse can only cover one electronic state (special pair), quantum beats result from a generation of the vibrational coherence. However, the system also exhibits single-vibronic ET. In this case, the coupled-master equations can be written as... 

The effects of the vibronic coupling competing with vibrational and/or vibronic relaxation on the femtosecond pump-probe stimulated emission spectra of molecules in condensed phases have been investigated. Taking into account vibronic and vibrational relaxation and vibronic coupling in molecular terms, the coupled master equations have been briefly derived for... 

Although the presented numerical approach to the coupled master equations has shown that a turnover feature can be seen in vibronic dynamics appearing in the calculated pump-probe stimulated emission spectra as a function of the energy gap between the two relevant vibronic states. It is found that vibronic quantum beats cannot be observed when the energy gap becomes larger in which situation it leads to smaller Franck-Condon overlaps between the energy conserved levels. 

Although a theoretical approach has been desecrated as to how one can apply the generalized coupled master equations to deal with ultrafast radiationless transitions taking place in molecular systems, there are several problems and limitations to the approach. For example, the number of the vibrational modes is limited to less than six for numerical calculations. This is simply just because of the limitation of the computational resources. If the efficient parallelization can be realized to the generalized coupled master equations, the limitation of the number of the modes can be relaxed. In the present approach, the Markov approximation to the interaction between the molecule and the heat bath mode has been employed. If the time scale of the ultrashort measurements becomes close to the characteristic time of the correlation time of the heat bath mode, the Markov approximation cannot be applicable. In this case, the so-called non-Markov treatment should be used. This, in turn, leads to a more computationally demanding task. Thus, it is desirable to develop a new theoretical approach that allows a more efficient algorithm for the computation of the non-Markov kernels. Another problem is related to the modeling of the interaction between the molecule and the heat bath mode. In our model, the heat bath mode is treated as... 

Apart from the heat bath mode, the harmonic potential surface model has been used for the molecular vibrations. It is possible to include the generalized harmonic potential surfaces, i.e., displaced-distorted-rotated surfaces. In this case, the mode coupling can be treated within this model. Beyond the generalized harmonic potential surface model, there is no systematic approach in constructing the generalized (multi-mode coupled) master equation that can be numerically solved. The first step to attack this problem would start with anharmonicity corrections to the harmonic potential surface model. Since anharmonicity has been recognized as an important mechanism in the vibrational dynamics in the electronically excited states, urgent realization of this work is needed. 

To solve the generalized coupled master equations such as Eqs. (142)-(144) numerically, what algorism can be used ... 

Generalized first-order kinetics have been extensively reviewed in relation to teclmical chemical applications [59] and have been discussed in the context of copolymerization [53]. From a theoretical point of view, the general class of coupled kinetic equation (A3.4.138) and equation (A3.4.139) is important, because it allows for a general closed-fomi solution (in matrix fomi) [49]. Important applications include the Pauli master equation for statistical mechanical systems (in particular gas-phase statistical mechanical kinetics) [48] and the investigation of certain simple reaction systems [49, ]. It is the basis of the many-level treatment of... 

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. 

For the weak coupling case with Eq. (32), our master equation reduces to the well-known quantum master equation, obtained through the approximation, widely used in quantum optics. This equation describes, among other things, quantum decoherence due to Brownian motion. Hence, we have derived an exact quantum master equation for the transformed density operator p that describes exact decoherence. Furthermore, our master equation cannot keep the purity of the transformed density matrix. Indeed, one can show that if p(t) is factorized into a product of transformed wave functions at t = 0, it will not be factorized into their product for t > 0. This is consistent the nondistributivity of the nonunitary transformation (18). 

Transition state theory yields rate coefficients at the high-pressure limit (i.e., statistical equilibrium). For reactions that are pressure-dependent, more sophisticated methods such as RRKM rate calculations coupled with master equation calculations (to estimate collisional energy transfer) allow for estimation of low-pressure rates. Rate coefficients obtained over a range of temperatures can be used to obtain two- and three-parameter Arrhenius expressions ... 

The chemist s view of a reaction is phenomenological. One assumes the existence of reactants, labeled a and products labeled b. The time evolution of normalized reactant (na) and product (nt) populations, na(t) + nb(t) = 1, is described by the coupled set of master equations ... 

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. 

Another, even simpler choice for is the two-valued Markov process (IV.2.3). The joint master equation reduces to two coupled equations for the pair of singlevariable functions (y, 1, t) = P (y, t),... 

Note here that the relation between mesoscopic and microscopic approaches is not trivial. In fact, the former is closer to the macroscopic treatment (Section 2.1.1) which neglects the structural characteristics of a system. Passing from the micro- to meso- and, finally, to macroscopic level we loose also the initial statement of a stochastic model of the Markov process. Indeed, the disadvantages of deterministic equations used for rather simplified treatment of bimolecular kinetics (Section 2.1) lead to the macro- and mesoscopic models (Section 2.2) where the stochasticity is kept either by adding the stochastic external forces (Section 2.2.1) or by postulating the master equation itself for the relevant Markov process (Section 2.2.2). In the former case the fluctuation source is assumed to be external, whereas in the latter kinetics of bimolecular reaction and fluctuations are coupled and mutually related. Section 2.3.1.2 is aimed to consider the relation between these three levels as well as to discuss problem of how determinicity and stochasticity can coexist. 

A structure of the obtained set of equations derived by us in [81, 86] is very close to the famous BBGKI set of equations widely used in the statistical physics of dense gases and liquids [76]. Therefore, we presented the master equation of the Markov process in a form of the infinite set of deterministic coupled equations for averages (equation (2.3.34)). Practical use of these equations requires us to reduce them, retaining the joint correlation functions only. 

To formulate this stochastic model in terms of concentrations and joint correlation functions only, i.e., in a manner we used earlier in Chapters 2, 4 and 5, it is convenient to write down a master equation of the Markov process under study in a form of the infinite set of coupled equations for many-point densities. Let us write down the first equations for indices (m + m ) = 1 ... 

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. 

The essential progress in calculation of transport properties in the strong electron-vibron interaction limit has been made with the help of the master equation approach [104-112]. This method, however, is valid only in the limit of very weak molecule-to-lead coupling and neglects all spectral effects, which are the most important at finite coupling to the leads. 

At strong coupling to the leads and the finite level width the master equation approach can no longer be used, and we apply alternatively the nonequilibrium Green function technique which have been recently developed to treat vibronic effects in a perturbative or self-consistent way in the cases of weak and intermediate electron-vibron interaction [113-130]. 

When the coupling to the leads is weak, electron-electron interaction results in Coulomb blockade, the sequential tunneling is described by the master equation method [169-176] and small cotunneling current in the blockaded regime can be calculated by the next-order perturbation theory [177-179], This theory was used successfully to describe electron tunneling via discrete... 

In these review we consider different methods. The density matrix can be determined from the master equation. For Green functions the EOM method or Keldysh method can be applied. Traditionally, the density matrix is used in the case of very weak system-to-lead coupling, while the NGF methods are more successful in the description of strong and intermediate coupling to the leads. The convenience of one or other method is determined essentially by the type of interaction. Our aim is to combine the advantages of both methods. 

It is quite clear from the presented figures that our Ansatz and the master equation method give essentially the same results in the limit of weak coupling... 

To test our method, we have analyzed the CB stability diagrams for a SSJ and a DSJ. Our results are all consistent with the results of experiments and the master-equation approach. We showed, that the improved lesser Green function gives better results for weak molecule-to-contact couplings, where a comparison with the master equation approach is possible. 

Open quantum systems have attracted much attention over the last decades. While most of the studies dealt with systems coupled to bosonic heat baths, recently systems coupled to fermionic reservoirs describing for example molecular wires have been in the focus of many investigations. This chapter will not try to give a concise overview of the available literature but will focus on a particular approach time-local (TL) quantum master equations (QMEs) and in particular their combination with specific forms of the spectral density. 

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