Classical Master Equation Research Articles

Noise-induced transport in the Aubry-André-Harper model

We study quantum transport in a quasiperiodic Aubry-André-Harper (AAH) model induced by the coupling of the system to a Markovian heat bath. We find that coupling the heat bath locally does not affect transport in the delocalized and critical phases, while it induces logarithmic transport in the localized phase. Increasing the number of coupled sites at the central region introduces a transient diffusive regime, which crosses over to logarithmic transport in the localized phase and in the delocalized regime to ballistic transport. On the other hand, when the heat bath is coupled to equally spaced sites of the system, we observe a crossover from ballistic and logarithmic transport to diffusion in the delocalized and localized regimes, respectively. We propose a classical master equation, which in the localized phase, captures our numerical observations for both coupling configurations on a qualitative level and for some parameters, even on a quantitative level. Using the classical picture, we show that the crossover to diffusion occurs at a time that increases exponentially with the spacing between the coupled sites, and the resulting diffusion constant decreases exponentially with the spacing.

Adiabatic theorem for classical stochastic processes

We apply adiabatic theorems developed for quantum mechanics to stochastic annealing processes described by the classical master equation with a time-dependent generator. When the instantaneous stationary state is unique and the minimum decay rate g is nonzero, the time-evolved state is basically relaxed to the instantaneous stationary state. By formulating an asymptotic expansion rigorously, we derive conditions for the annealing time τ that the state is close to the instantaneous stationary state. Depending on the time dependence of the generator, typical conditions are written as τ>const.×g−α with 1⩽α⩽2 . We also find that a rigorous treatment gives the scaling τ>const.×g−2|ln⁡g| .

Generalized free energy and dynamical state transition of the dyonic AdS black hole in the grand canonical ensemble

We study the generalized free energy of the dyonic AdS black hole in an ensemble with varying electric charge qE and fixed magnetic charge qM. When we adjust the temperature T and the electric potential ΦE of the ensemble, the Ricci scalar curvature R and electromagnetic potential Au usually diverge at the horizon. We regularize them and incorporate the off-shell corrections into the Einstein-Hilbert action. Alternatively, we find that the off-shell corrections can also be obtained by adding a boundary near the horizon to exclude the singularities. Ultimately, we derive the generalized free energy which is consistent with the definition of the thermodynamic relations. Based on the generalized free energy landscape, we can describe the dynamics of state transition as a stochastic process quantified by the Langevin equation. The path integral framework can be formulated to derive the time-dependent trajectory of the order parameter and the time evolution of the transition probability. By comparing the probability with the result of the classical master equation, we attribute the contribution to the probability of one pseudomolecule or antipseudomolecule (the instanton and anti-instanton pairs) to the rate of state transition. These results are consistent with the qualitative analysis of the free energy landscape.

Joining Landauer approach and classical multi electronic master-equation description in nanoscale transport for non-interactive systems

In this work we show that in the non-interacting limit, i.e., when the electronic structure of the N-particle states is frozen, in the wide-band limit (WBL) approximation, the classical master equation (CME) with the electron transfer rates obtained via Fermi golden rule and the elastic scattering approach (ES) are equivalent. This fact is encouraging, since it allows the insertion of elastic mechanisms into quantum transport via the CME approach thus, describing weak and strong quantum transport regimes on an equal footing within this theory.

Quantum master equation for the vacuum decay dynamics

The quantum master equation required to describe the dynamics of gravity-related vacuum decay is still challenging. We aim to study this issue. Our model consists of the spacetime and scalar field with self-interaction potential. The environment is chosen as spacetime while the system is formed by the vacua of the scalar field. We demonstrate that the quantum dynamics of the vacua can be described by the Redfield equation, which can depict the evolution of both coherence and the comoving volume fraction of the vacuum. Under the Markovian limit, coherence monotonically decreases with time, leading to the initial quantum state to decohere into a classical state. This helps the understanding of the decoherence of the universe. We also highlight that in certain circumstances, the evolution of the vacuum system may display non-Markovian dynamics. In specific scenarios, the classical limit of the quantum master equation is consistent with the classical master equation. In the steady state, the dominant vacuum corresponds to the smallest cosmological constant, and various dS vacua can reach equilibrium states.

Nonadiabatic dynamics near metal surfaces under Floquet engineering: Floquet electronic friction vs Floquet surface hopping.

In the previous study Wang and Dou [J. Chem. Phys. 158, 224109 (2023)], we have derived a Floquet classical master equation (FCME) to treat nonadiabatic dynamics near metal surfaces under Floquet engineering. We have also proposed a trajectory surface hopping algorithm to solve the FCME. In this study, we map the FCME into a Floquet Fokker-Planck equation in the limit of fast Floquet driving and fast electron motion as compared to nuclear motion. The Fokker-Planck equation is then being solved using Langevin dynamics with explicit friction and random force from the nonadiabatic effects of hybridized electrons and Floquet states. We benchmark the Floquet electronic friction dynamics against Floquet quantum master equation and Floquet surface hopping. We find that Floquet driving results in a violation of the second fluctuation-dissipation theorem, which further gives rise to heating effects.

Deviations and similarities between landauer’s approach and the multi-electronic classical master equation in describing nanoscale transport

In this work, we show that the classical master equation (CME) treatment—with the rates obtained via the Fermi golden rule—and the elastic scattering (ES) approach give the same results for a system composed of two states/one level when considering the approximations of (i) non-interacting limit, i.e., the electronic structure of the N-particle states remains frozen even in the presence of an extra particle, (ii) wide-band limit (WBL) approximation, and (iii) excited states are discarded. Although the predictions of these two approaches ‘deviate’ from each other when more states and/or levels are considered, under the conditions of strong coupling limit and symmetric contacts both treatments capture the same physics involved in the transport process. For other situations—such as asymmetric coupling and/or weak metal–organic coupling—the predictions of these two theories do not agree with each other. Finally, even considering that in our treatment the electronic structure of the system is described at a tight binding level, the corresponding results clearly show the situations where the similarities and differences between the CME and ES approaches can be identified.

Anomalous Diffusion in the Long-Range Haken-Strobl-Reineker Model.

We analyze the propagation of excitons in a d-dimensional lattice with power-law hopping ∝1/r^{α} in the presence of dephasing, described by a generalized Haken-Strobl-Reineker model. We show that in the strong dephasing (quantum Zeno) regime the dynamics is described by a classical master equation for an exclusion process with long jumps. In this limit, we analytically compute the spatial distribution, whose shape changes at a critical value of the decay exponent α_{cr}=(d+2)/2. The exciton always diffuses anomalously: a superdiffusive motion is associated to a Lévy stable distribution with long-range algebraic tails for α≤α_{cr}, while for α>α_{cr} the distribution corresponds to a surprising mixed Gaussian profile with long-range algebraic tails, leading to the coexistence of short-range diffusion and long-range Lévy flights. In the many-exciton case, we demonstrate that, starting from a domain-wall exciton profile, algebraic tails appear in the distributions for any α, which affects thermalization: the longer the hopping range, the faster equilibrium is reached. Our results are directly relevant to experiments with cold trapped ions, Rydberg atoms, and supramolecular dye aggregates. They provide a way to realize an exclusion process with long jumps experimentally.

Assessing Mixed Quantum-Classical Molecular Dynamics Methods for Nonadiabatic Dynamics of Molecules on Metal Surfaces.

Mixed quantum-classical (MQC) methods for simulating the dynamics of molecules at metal surfaces have the potential to accurately and efficiently provide mechanistic insight into reactive processes. Here, we introduce simple two-dimensional models for the scattering of diatomic molecules at metal surfaces based on recently published electronic structure data. We apply several MQC methods to investigate their ability to capture how nonadiabatic effects influence molecule-metal energy transfer during the scattering process. Specifically, we compare molecular dynamics with electronic friction, Ehrenfest dynamics, independent electron surface hopping, and the broadened classical master equation approach. In the case of independent electron surface hopping, we implement a simple decoherence correction approach and assess its impact on vibrationally inelastic scattering. Our results show that simple, low-dimensional models can be used to qualitatively capture experimentally observed vibrational energy transfer and provide insight into the relative performance of different MQC schemes. We observe that all approaches predict similar kinetic energy dependence but return different vibrational energy distributions. Finally, by varying the molecule-metal coupling, we can assess the coupling regime in which some MQC methods become unsuitable.

Nonadiabatic dynamics near metal surface with periodic drivings: A Floquet surface hopping algorithm.

We develop a Floquet surface hopping approach to deal with nonadiabatic dynamics of molecules near metal surfaces subjected to time-periodic drivings from strong light-matter interactions. The method is based on a Floquet classical master equation (FCME) derived from a Floquet quantum master equation (FQME), followed by a Wigner transformation to treat nuclear motion classically. We then propose different trajectory surface hopping algorithms to solve the FCME. We find that a Floquet averaged surface hopping with electron density (FaSH-density) algorithm works the best as benchmarked with the FQME, capturing both the fast oscillations due to the driving and the correct steady-state observables. This method will be very useful to study strong light-matter interactions with a manifold of electronic states.

Topological Dirac sigma models and the classical master equation

We present the construction of the classical Batalin–Vilkovisky (BV) action for topological Dirac sigma models. The latter are two-dimensional topological field theories that simultaneously generalise the completely gauged Wess–Zumino–Novikov–Witten model and the Poisson sigma model. Their underlying structure is that of Dirac manifolds associated to maximal isotropic and integrable subbundles of an exact Courant algebroid twisted by a 3-form. In contrast to the Poisson sigma model, the AKSZ construction is not applicable for the general Dirac sigma model. We therefore follow a direct approach for determining a suitable BV extension of the classical action functional with ghosts and antifields satisfying the classical master equation. Special attention is paid to target space covariance, which requires the introduction of two connections with torsion on the Dirac structure.

Intrinsic timing in classical master equation dynamics from an extended quadratic format of the evolution law

Intrinsic timing in classical master equation dynamics from an extended quadratic format of the evolution law

Convergence condition of simulated quantum annealing for closed and open systems

Simulated quantum annealing is a generic classical protocol to simulate some aspects of quantum annealing and is sometimes regarded as a classical alternative to quantum annealing in finding the ground state of a classical Ising model. We derive a generic condition for simulated quantum annealing to converge to thermal equilibrium at a given, typically low, temperature. Both closed and open systems are treated. We rewrite the classical master equation for simulated quantum annealing into an imaginary-time Schr\"odinger equation, to which we apply the imaginary-time variant of asymptotic adiabatic condition to deduce the convergence condition. The result agrees qualitatively with a rigorous convergence condition of simulated quantum annealing for closed systems, which was derived from the theory of inhomogeneous Markov process. Also observed is qualitative agreement with a rigorous convergence condition of quantum annealing for closed systems under the real-time Schr\"odinger dynamics. This coincidence of convergence conditions for classical stochastic processes for simulated quantum annealing and the real-time quantum dynamics for quantum annealing is highly non-trivial and calls for further scrutiny.

Noise and thermodynamic uncertainty relation in "underwater" molecular junctions.

We determine the zero-frequency charge current noise in a metal-molecule-metal junction embedded in a thermal environment, e.g., a solvent, dominated by sequential charge transmission described by a classical master equation, and we study the dependence of specific model parameters, i.e., the environmental reorganization energy and relaxation behavior. Interestingly, the classical current noise term has the same structure as its quantum analog, which reflects a charge correlation due to the bridging molecule. We further determine the thermodynamic uncertainty relation (TUR) defininig a bound on the relationship between the average charge current, its fluctuation, and the entropy production in an electrochemical junction in the Marcus regime. In the second part, we use the same methodology to calculate the current noise and the TUR for a protoype photovoltaic cell in order to predict its upper bound for the efficiency of energy conversion into useful work.

The BV action of 3D twisted R-Poisson sigma models

We determine the solution to the classical master equation for a 3D topological field theory with Wess-Zumino term and an underlying geometrical structure of a twisted R-Poisson manifold on its target space. The graded geometry of the target space departs from the usual QP structure encountered in the AKSZ construction of topological sigma models, the obstruction being attributed to the presence of the Wess-Zumino 4-form. Due to the inapplicability of the AKSZ construction in this case, we set up the traditional BV/BRST formalism for twisted R-Poisson sigma models in any dimension, which feature an open gauge algebra and constitute multiple stages reducible constrained Hamiltonian systems. An unusual feature of the theories is that they exhibit non-linear openness of the gauge algebra, in other words products of the equations of motion appear in them. Nevertheless, we find the BV action in presence of the 4-form twist in 3D, namely for a specific 4-form twisted (pre-)Courant sigma model. Moreover, we provide a complete set of explicit formulas for the off-shell nilpotent BV operator for untwisted R-Poisson sigma models in any dimension.

Consistent Deformations for a Non-Standard D = 6 Topological BF Model from a BRST-Symmetry-Based Cohomological Approach

This paper falls under the heading of constructing consistent self-couplings in topological BF models. Our endeavor is of interest in the context of pure gravity, General Relativity, and super-gravity in Ashtekar formalism, which allow for certain economic formulations in terms of self-coupled BF theories in the presence of certain extra-constraints. More precisely, herein we address the construction of a special class of D=6 self-interactions for a collection of topological BF models with a non-standard field spectrum. Our methodology relies on a deformation method based on the relationship between antifield–BRST symmetry and the non-trivial gauge symmetries of a given field theory and implemented via the computation of certain precise spaces of the local BRST cohomology corresponding to the free limit. This cohomological BRST approach is applied to the starting free model under standard “selection rules” from Quantum Field Theory. Our findings are completely new and reveal a self-interacting topological BF model in D=6 with a complex gauge structure that is entirely read from the expression of the fully deformed solution to the classical master equation (the canonical generator of the antifield–BRST symmetry), and includes a generalization of the famous D=2 gravity in BF formulation.

Dynamical Lee-Yang zeros for continuous-time and discrete-time stochastic processes.

We describe classical stochastic processes by using dynamical Lee-Yang zeros. The system is in contact with external leads and the time evolution is described by the two-state classical master equation. The cumulant generating function is written in a factorized form and the current distribution is characterized by the dynamical Lee-Yang zeros. We show that a continuous distribution of zeros is obtained by discretizing the time variable. When the transition probability is a periodically oscillating function of time, the distribution of zeros splits into many parts. We study the geometric property of the current by comparing the result with that of the adiabatic approximation. We also use the Floquet-Magnus expansion in the continuous-time case to study dynamical effects on the current at the fast-driving regime.

Classical master equations and broadened classical master equations: Some analytical results.

Some analytical results for the steady-state properties of the single-molecule tunneling junction are obtained with the use of the broadened classical master equations and classical master equations. The case of the one electronic level of the bridge molecule coupled to a single classical harmonic oscillator is considered within the spin-less model. Based on these equations, we establish some relations between different average values of interest, considering the large bias limit and the limit of the weak electron-oscillator coupling. We derive the analytical expressions for a number of characteristic properties of the tunneling junction in these limiting cases, compare our results with those obtained by the numerically exact calculations, and find that our expressions work very well. In the diabatic regime, the approximate solutions of the classical master equations are suggested, which permit us to introduce the effective temperature Teff and perform rather simple calculations of the average vibrational excitations N and the tunnel current I. It is shown that in the adiabatic regime, the properties of the tunneling junction depend essentially on the effective temperature Teff ad. We obtain the analytical expressions for Teff ad using different approaches for the treatment of the adiabatic regime. For both the diabatic and adiabatic regimes, we calculate Teff, Teff ad, N, and I, compare our results with those available in the literature, and confirm well agreement. The dependence of N and I on the reorganization energy and the position of the electronic level of the bridge molecule is discussed.

Fully Quantum Modeling of Exciton Diffusion in Mesoscale Light Harvesting Systems.

It has long been a challenge to accurately and efficiently simulate exciton–phonon dynamics in mesoscale photosynthetic systems with a fully quantum mechanical treatment due to extensive computational resources required. In this work, we tackle this seemingly intractable problem by combining the Dirac–Frenkel time-dependent variational method with Davydov trial states and implementing the algorithm in graphic processing units. The phonons are treated on the same footing as the exciton. Tested with toy models, which are nanoarrays of the B850 pigments from the light harvesting 2 complexes of purple bacteria, the methodology is adopted to describe exciton diffusion in huge systems containing more than 1600 molecules. The superradiance enhancement factor extracted from the simulations indicates an exciton delocalization over two to three pigments, in agreement with measurements of fluorescence quantum yield and lifetime in B850 systems. With fractal analysis of the exciton dynamics, it is found that exciton transfer in B850 nanoarrays exhibits a superdiffusion component for about 500 fs. Treating the B850 ring as an aggregate and modeling the inter-ring exciton transfer as incoherent hopping, we also apply the method of classical master equations to estimate exciton diffusion properties in one-dimensional (1D) and two-dimensional (2D) B850 nanoarrays using derived analytical expressions of time-dependent excitation probabilities. For both coherent and incoherent propagation, faster energy transfer is uncovered in 2D nanoarrays than 1D chains, owing to availability of more numerous propagating channels in the 2D arrangement.

On a gauge-invariant deformation of a classical gauge-invariant theory

We consider a general gauge theory with independent generators and study the problem of gauge-invariant deformation of initial gauge-invariant classical action. The problem is formulated in terms of BV-formalism and is reduced to describing the general solution to the classical master equation. We show that such general solution is determined by two arbitrary generating functions of the initial fields. As a result, we construct in explicit form the deformed action and the deformed gauge generators in terms of above functions. We argue that the deformed theory must in general be non-local. The developed deformation procedure is applied to Abelian vector field theory and we show that it allows to derive non-Abelain Yang-Mills theory. This procedure is also applied to free massless integer higher spin field theory and leads to local cubic interaction vertex for such fields.