Redfield Equation Research Articles

Hierarchical equations of motion for multiple baths (HEOM-MB) and their application to Carnot cycle.

We have developed a computer code for the thermodynamic hierarchical equations of motion derived from a spin subsystem coupled to multiple Drude baths at different temperatures, which are connected to or disconnected from the subsystem as a function of time. The code can simulate the reduced dynamics of the subsystem under isothermal, isentropic, thermostatic, and entropic conditions. The extensive and intensive thermodynamic variables are calculated as physical observables, and Gibbs and Helmholtz energies are evaluated as intensive and extensive work. The energy contribution of the system-bath interaction is evaluated separately from the subsystem using the hierarchical elements of the hierarchical equations of motion. The accuracy of the calculated results for the equilibrium distribution and the two-body correlation functions is assessed by contrasting the results with those obtained from the time-convolution-less Redfield equation. It is shown that the Lindblad master equation is inappropriate for the thermodynamic description of a spin-boson system. Non-Markovian effects in thermostatic processes are investigated by sequentially turning on and off the baths at different temperatures with different switching times and system-bath coupling. In addition, the Carnot cycle is simulated under quasi-static conditions. To analyze the work performed for the subsystem in the cycle, thermodynamic work diagrams are plotted as functions of intensive and extensive variables. The C++ source codes are provided as supplementary material.

Polariton-assisted incoherent to coherent excitation energy transfer between colloidal nanocrystal quantum dots.

We explore the dynamics of energy transfer between two nanocrystal quantum dots placed within an optical microcavity. By adjusting the coupling strength between the cavity photon mode and the quantum dots, we have the capacity to fine-tune the effective coupling between the donor and acceptor. Introducing a non-adiabatic parameter, γ, governed by the coupling to the cavity mode, we demonstrate the system's capability to shift from the overdamped Förster regime (γ ≪ 1) to an underdamped coherent regime (γ ≫ 1). In the latter regime, characterized by swift energy transfer rates, the dynamics are influenced by decoherence time. To illustrate this, we study the exciton energy transfer dynamics between two closely positioned CdSe/CdS core/shell quantum dots with sizes and separations relevant to experimental conditions. Employing an atomistic approach, we calculate the excitonic level arrangement, exciton-phonon interactions, and transition dipole moments of the quantum dots within the microcavity. These parameters are then utilized to define a model Hamiltonian. Subsequently, we apply a generalized non-Markovian quantum Redfield equation to delineate the dynamics within the polaritonic framework.

Unfolding system-environment correlation in open quantum systems: Revisiting master equations and the Born approximation

Understanding system-environment correlations in open quantum systems is vital for various quantum information and technology applications. However, these correlations are often overlooked or hidden in derivations of open-quantum-system master equations, especially when applying the Born approximation. To address this issue, given a microscopic model, we demonstrate how to retain system-environment correlation within commonly used master equations, such as the Markovian Lindblad, Redfield, second-order time convolutionless, second-order Nakajima-Zwanzig, and second-order universal Lindblad-like equations. We show that each master equation corresponds to a particular approximation on the system-environment correlation operator. In particular, our analysis exposes the form of the hidden system-environment correlation in the Markovian Lindblad equation derived using the Born approximation. We also identify that the processes leading to the Redfield equation yield an inaccurate initial-time system-environment correlation approximation. By fixing this problem, we propose a corrected Redfield equation with an improved prediction for early stages of the time evolution. We further illustrate our results in two examples, which imply that the second-order universal Lindblad-like equation captures correlation more accurately than the other standard master equations. Published by the American Physical Society 2024

Gate‐Based Protocol Simulations for Quantum Repeaters using Quantum‐Dot Molecules in Switchable Electric Fields

AbstractElectrically controllable quantum‐dot molecules (QDMs) are a promising platform for deterministic entanglement generation and, as such, a resource for quantum‐repeater networks. A microscopic open‐quantum‐systems approach based on a time‐dependent Bloch–Redfield equation is developed to model the generation of entangled spin states with high fidelity. The state preparation is a crucial step in a protocol for deterministic entangled‐photon‐pair generation that is proposed for quantum repeater applications. The theory takes into account the quantum‐dot molecules' electronic properties that are controlled by time‐dependent electric fields as well as dissipation due to electron–phonon interaction. The transition between adiabatic and non‐adiabatic regimes is quantified, which provides insights into the dynamics of adiabatic control of QDM charge states in the presence of dissipative processes. From this, the maximum speed of entangled‐state preparation is inferred under different experimental conditions, which serves as a first step toward simulation of attainable entangled photon‐pair generation rates. The developed formalism opens the possibility for device‐realistic descriptions of repeater protocol implementations.

Quantum Trajectories for Time-Local Non-Lindblad Master Equations.

For the efficient simulation of open quantum systems, we often use quantum jump trajectories given by pure states that evolve stochastically to unravel the dynamics of the underlying master equation. In the Markovian regime, when the dynamics is described by a Gorini-Kossakowski-Sudarshan-Lindblad (GKSL) master equation, this procedure is known as MonteCarlo wave function approach. However, beyond ultraweak system-bath coupling, the dynamics of the system is not described by an equation of GKSL type, but rather by the Redfield equation, which can be brought into pseudo-Lindblad form. Here, negative dissipation strengths prohibit the conventional approach. To overcome this problem, we propose a pseudo-Lindblad quantum trajectory (PLQT) unraveling. It does not require an effective extension of the state space, like other approaches, except for the addition of a single classical bit. We test the PLQT for the eternal non-Markovian master equation for a single qubit and an interacting Fermi-Hubbard chain coupled to a thermal bath and discuss its computational effort compared to solving the full master equation.

A time-dependent regularization of the Redfield equation

We introduce a new regularization of the Redfield equation based on a replacement of the Kossakowski matrix with its closest positive semidefinite neighbor. Unlike most of the existing approaches, this procedure is capable of retaining the time dependence of the Kossakowski matrix, leading to a completely positive divisible quantum process. Using the dynamics of an exactly-solvable three-level open system as a reference, we show that our approach performs better during the transient evolution, if compared to other approaches like the partial secular master equation or the universal Lindblad equation. To make the comparison between different regularization schemes independent from the initial state, we introduce a new quantitative approach based on the Choi-Jamiołkowski isomorphism.

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.

Full counting statistics and coherences: Fluctuation symmetry in heat transport with the unified quantum master equation.

Recently, a "unified" quantum master equationwas derived and shown to be of the Gorini-Kossakowski-Lindblad-Sudarshan form. This equationdescribes the dynamics of open quantum systems in a manner that forgoes the full secular approximation and retains the impact of coherences between eigenstates close in energy. We implement full counting statistics with the unified quantum master equationto investigate the statistics of energy currents through open quantum systems with nearly degenerate levels. We show that, in general, this equationgives rise to dynamics that satisfy fluctuation symmetry, a sufficient condition for the Second Law of Thermodynamics at the level of average fluxes. For systems with nearly degenerate energy levels, such that coherences build up, the unified equation is simultaneously thermodynamically consistent and more accurate than the fully secular master equation. We exemplify our results for a "V" system facilitating energy transport between two thermal baths at different temperatures. We compare the statistics of steady-state heat currents through this system as predicted by the unified equationto those given by the Redfield equation, which is less approximate but, in general, not thermodynamically consistent. We also compare results to the secular equation, where coherences are entirely abandoned. We find that maintaining coherences between nearly degenerate levels is essential to properly capture the current and its cumulants. On the other hand, the relative fluctuations of the heat current, which embody the thermodynamic uncertainty relation, display inconsequential dependence on quantum coherences.

NMR Relaxation by Redfield equation in a spin system [formula omitted

The Redfield master equation was solved analytically for a nuclear system with spin I=7/2. Using the irreducible tensor operator basis, the solutions of each density matrix element were computed. The experimental setup consisted of the 133Cs nuclei of the cesium-pentadecafluorooctanoate molecule in a lyotropic liquid crystal sample in the nematic phase at room temperature. Experimental longitudinal and transverse magnetization dynamics of the 133Cs nuclei were monitored, and the theoretical approach was used to generate valuable mathematical expressions with the highest accuracy through numerical procedures. This methodology can be extended to other nuclei with minimal difficulties.

Effective master equations for two accelerated qubits

We revisit the problem involving two constantly accelerating Unruh-DeWitt detectors using Open Effective Field Theory methods. We study the time evolution of the joint detector state using a Markovian approximation which differs from the standard one taken in the literature. We show that this Markovian limit already implies the complete positivity of the dynamical evolution map without invoking the rotating wave approximation (RWA), in contrast to standard derivations of open system master equations. By calculating explicitly the domain of validity of this Markovian approximation, we argue that the lack of complete positivity in the usual microscopic derivation stems from the (subtle) fact that the Redfield equation is used outside its domain of validity. We give two well-known cases studied in the literature that violate the validity of the Markovian approximation: (i) the ``stacked trajectory'' limit (when detector trajectories are taken to be on top of one another), and (ii) large gap-to-acceleration ratio. Since Markovian dynamics with or without RWA can lead to different qualitative predictions for entanglement dynamics, our work emphasizes the need to properly track the regime of validity of all approximations.

An examination of phonon-inelastic molecule-metal scattering using reduced density matrix and stochastic wave packet methods.

We explore the application of reduced density matrix-based approaches to molecules interacting with the lattice vibrations of metals, an interaction responsible for the temperature dependence of many of the fundamental steps of catalysis. We avoid the use of simple models for the bath and instead use density functional theory to compute all molecule-phonon interactions and the properties of the lattice phonons, for methane scattering from Ir(111). We find that while the large metal mass leads to long bath correlation times, these are not significantly longer than the time over which the reduced density matrix changes due to interactions with the bath. We show that the neglect of memory is reasonable and the use of the Redfield equation is justified. We also show how the commonly used rotating wave approximation is far too severe for this scattering problem. A less restrictive approximation that is nearly exact for our system gives an equation of motion in the Lindblad form. As a result, the Monte Carlo wave packet methods can be used to describe gas-phonon scattering, guaranteeing positivity, and with all couplings derived from first-principles.

Thermodynamic consistency of quantum master equations

Starting from a microscopic system-baths description, we derive the general conditions for a time-local quantum master equation (QME) to satisfy the first and second law of thermodynamics at the fluctuating level. Using counting statistics, we show that the fluctuating second law can be rephrased as a Generalized Quantum Detailed Balance condition (GQDB), i.e., a symmetry of the time-local generators which ensures the validity of the fluctuation theorem. When requiring in addition a strict system-bath energy conservation, the GQDB reduces to the usual notion of detailed balance which ensures QMEs with Gibbsian steady states. However, if energy conservation is only required on average, QMEs with non Gibbsian steady states can still maintain a certain level of thermodynamic consistency. Applying our theory to commonly used QMEs, we show that the Redfield equation breaks the GQDB, and that some recently derived approximation schemes based on the Redfield equation (which hold beyond the secular approximation and allow to derive a QME of Lindblad form) satisfy the GQDB and the average first law. We find that performing the secular approximation is the only way to ensure the first and second law at the fluctuating level.

Perturbative steady states of completely positive quantum master equations.

The Lindblad form guarantees complete positivity of a Markovian quantum master equation(QME). However, its microscopic derivation for a quantum system weakly interacting with a thermal bath requires several approximations, which may result in inaccuracies in the QME. Recently, various Lindbladian QMEs were derived without resorting to the secular approximation from the Redfield equation which does not guarantee the complete positivity. Here we explicitly calculate, in a perturbative manner, the equilibrium steady states of these Lindbladian QMEs. We compare the results with the steady state of the Redfield equation obtained from an analytic continuation method, which coincides with the so-called mean force Gibbs (MFG) state. The MFG state is obtained by integrating out the bath degrees of freedom for the Gibbs state of the total Hamiltonian. We explicitly show that the steady states of the Lindbladian QMEs are different from the MFG state. Our results indicate that manipulations of the Redfield equationneeded to enforce complete positivity of a QME drives its steady state away from the MFG state. We also find that, in the high-temperature regime, both the steady states of the Lindbladian QMEs and MFG state reduce to the same Gibbs state of a system Hamiltonian under certain conditions.

Geometric-arithmetic master equation in large and fast open quantum systems

Understanding nonsecular dynamics in open quantum systems is addressed here, with emphasis on systems with large numbers of Bohr frequencies, zero temperature, and fast driving. We employ the master equation, which replaces arithmetic averages of the decay rates in the open system, with their geometric averages, and find that it can improve the second order perturbation theory, known as the Redfield equation, while enforcing complete positivity on quantum dynamics. The characteristic frequency scale that governs the approximation is the minimax frequency: the minimum of the maximum system oscillation frequency and the bath relaxation rate; this needs to be larger than the dissipation rate for it to be valid. The concepts are illustrated on the Heisenberg ferromagnetic spin-chain model. To study the accuracy of the approximation, a Hamiltonian is drawn from the Gaussian unitary ensemble, for which we calculate the fourth order time-convolutionless master equation, in the Ohmic bath at zero temperature. Enforcing the geometric average, decreases the trace distance to the exact solution. Dynamical decoupling of a qubit is examined by applying the Redfield and the geometric-arithmetic master equations, in the interaction picture of the time dependent system Hamiltonian, and the results are compared to the exact path integral solution. The geometric-arithmetic approach is significantly simpler and can be super-exponentially faster compared to the Redfield approach.

Breakdown of the Weak-Coupling Limit in Quantum Annealing

Reverse annealing is a variant of quantum annealing, in which the system is prepared in a classical state, reverse-annealed to an inversion point, and then forward-annealed. We report on reverse annealing experiments using the D-Wave 2000Q device, with a focus on the $p=2$ $p$-spin problem, which undergoes a second order quantum phase transition with a gap that closes polynomially in the number of spins. We concentrate on the total and partial success probabilities, the latter being the probabilities of finding each of two degenerate ground states of all spins up or all spins down, the former being their sum. The empirical partial success probabilities exhibit a strong asymmetry between the two degenerate ground states, depending on the initial state of the reverse anneal. To explain these results, we perform open-system simulations using master equations in the limits of weak and strong coupling to the bath. The former, known as the adiabatic master equation (AME), with decoherence in the instantaneous energy eigenbasis, predicts perfect symmetry between the two degenerate ground states, thus failing to agree with the experiment. In contrast, the latter, known as the polaron transformed Redfield equation (PTRE), is in close agreement with experiment. Thus our results present a challenge to the sufficiency of the weak system-bath coupling limit in describing the dynamics of current experimental quantum annealers, at least for reverse annealing on timescales of a microsecond or longer.

Fundamental limitations in Lindblad descriptions of systems weakly coupled to baths

It is very common in the literature to write down a Markovian quantum master equation in Lindblad form to describe a system with multiple degrees of freedom and weakly connected to multiple thermal baths which can, in general, be at different temperatures and chemical potentials. However, the microscopically derived quantum master equation up to leading order in system-bath coupling is of the so-called Redfield form which is known to not preserve complete positivity in most cases. Additional approximations to the Redfield equation are required to obtain a Lindblad form. We lay down some fundamental requirements for any further approximations to Redfield equation, which, if violated, leads to physical inconsistencies like inaccuracies in the leading order populations and coherences in the energy eigenbasis, violation of thermalization, violation of local conservation laws at the non-equilibrium steady state (NESS). We argue that one or more of these conditions will generically be violated in all the weak system-bath-coupling Lindblad descriptions existing in literature to our knowledge. As an example, we study the recently derived Universal Lindblad Equation (ULE) and use these conditions to show violation of local conservation laws due to inaccurate coherences but accurate populations in energy eigenbasis. Finally, we exemplify our analytical results numerically in an interacting open quantum spin system.

Photoluminescence of Cis-Polyacetylene Semiconductor Material

Photoluminescence (PL) is one of the key experimental characterizations of optoelectronic materials, including conjugated polymers (CPs). In this study, a simplified model of an undoped cis-polyacetylene (cis-PA) oligomer was selected and used to explain the mechanism of photoluminescence (PL) of the CPs. Using a combination of the ab initio electronic structure and a time-dependent density matrix methodology, the photo-induced time-dependent excited state dynamics were computed. We explored the phonon-induced relaxation of the photoexcited state for a single oligomer of cis-PA. Here, the dissipative Redfield equation of the motion was used to compute the dissipative excited state dynamics of electronic degrees of freedom. This equation used the nonadiabatic couplings as parameters. The computed excited state dynamics showed that the relaxation rate of the electron is faster than the relaxation rate of the hole. The dissipative excited-state dynamics were combined with radiative recombination channels to predict the PL spectrum. The simulated results showed that the absorption and emission spectra both have a similar transition. The main result is that the computed PL spectrum demonstrates two mechanisms of light emission originating from (i) the inter-band transitions, corresponding to the same range of transition energies as the absorption spectrum and (ii) intra-band transitions not available in the absorption spectra. However, the dissipative Redfield equation of the motion was used to compute the electronic degrees of freedom of the nonadiabatic couplings, which helped to process the time propagation of the excited dynamic state. This excited dynamic state shows that the relaxation rate of the electron is faster than the relaxation rate of the hole, which can be used for improving organic semiconductor materials for photovoltaic and LED applications.

Relaxation of the Ising spin system coupled to a bosonic bath and the time dependent mean field equation.

The Ising model does not have strictly defined dynamics, only a spectrum. There are different ways to equip it with time dependence, e.g., the Glauber or the Kawasaki dynamics, which are both stochastic, but it means there is a master equation that can also describe their dynamics. These equations can be derived from the Redfield equation, where the spin system is weakly coupled to a bosonic bath. In this paper, we investigate the temperature dependence of the relaxation time of a Glauber-type master equation, especially in the case of the fully connected, uniform Ising model. The finite-size effects were analyzed with a reduced master equation and the thermodynamic limit with a time-dependent mean field equation.

Lindbladian approximation beyond ultraweak coupling

Away from equilibrium, the properties of open quantum systems depend on the details of their environment. A microscopic derivation of a master equation (ME) is therefore crucial. Of particular interest are Lindblad-type equations, not only because they provide the most general class of Markovian MEs, but also since they are the starting point for efficient quantum trajectory simulations. Lindblad-type MEs are commonly derived from the Born-Markov-Redfield equation via a rotating-wave approximation (RWA). However the RWA is valid only for ultraweak system-bath coupling and often fails to accurately describe nonequilibrium processes. Here we derive an alternative Lindbladian approximation to the Redfield equation, which does not rely on ultraweak system-bath coupling. Applying it to an extended Hubbard model coupled to Ohmic baths, we show that, especially away from equilibrium, it provides a good approximation in large parameter regimes where the RWA fails.

Local master equations bypass the secular approximation

Master equations are a vital tool to model heat flow through nanoscale thermodynamic systems. Most practical devices are made up of interacting sub-system, and are often modelled using either local master equations (LMEs) or global master equations (GMEs). While the limiting cases in which either the LME or the GME breaks down are well understood, there exists a 'grey area' in which both equations capture steady-state heat currents reliably, but predict very different transient heat flows. In such cases, which one should we trust? Here, we show that, when it comes to dynamics, the local approach can be more reliable than the global one for weakly interacting open quantum systems. This is due to the fact that the secular approximation, which underpins the GME, can destroy key dynamical features. To illustrate this, we consider a minimal transport setup and show that its LME displays exceptional points (EPs). These singularities have been observed in a superconducting-circuit realisation of the model \cite{partanen2019exceptional}. However, in stark contrast to experimental evidence, no EPs appear within the global approach. We then show that the EPs are a feature built into the Redfield equation, which is more accurate than the LME and the GME. Finally, we show that the local approach emerges as the weak-interaction limit of the Redfield equation, and that it entirely avoids the secular approximation.