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arXiv:1806.07540 · Chinese Journal of Chemical Physics

Exact generator and its high order expansions in time-convolutionless generalized master equation: Applications to spin-boson model and excitation energy transfer

Yanying Liu, Yaming Yan, Meng Xu, Kai Song, Qiang Shi

Published Aug 1, 2018• 15 citations
arXivHTMLPDF

Abstract

The time-convolutionless (TCL) quantum master equation provides a powerful tool to simulate reduced dynamics of a quantum system coupled to a bath. The key quantity in the TCL master equation is the so-called kernel or generator, which describes effects of the bath degrees of freedom. Since the exact TCL generators are usually hard to calculate analytically, most applications of the TCL generalized master equation have relied on approximate generators using second and fourth order perturbative expansions. By using the hierarchical equation of motion (HEOM) and extended HEOM methods, we present a new approach to calculating the exact TCL generator and its high order perturbative expansions. The new approach is applied to the spin-boson model with different sets of parameters, to investigate the convergence of the high order expansions of the TCL generator. We also discuss circumstances where the exact TCL generator becomes singular for the spin-boson model, and a model of excitation energy transfer in the Fenna-Matthews-Olson complex.

DOI
10.1063/1674-0068/31/cjcp1806146

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The time-convolutionless (TCL) quantum master equation provides a powerful tool to simulate reduced dynamics of a quantum system coupled to a bath. The key quantity in the TCL master equation is the so-called kernel or generator, which describes effects of the bath degrees of freedom. Since the exact TCL generators are usually hard to calculate analytically, most applications of the TCL generalized master equation have relied on approximate generators using second and fourth order perturbative expansions. By using the hierarchical equation of motion (HEOM) and extended HEOM methods, we present a new approach to calculating the exact TCL generator and its high order perturbative expansions. The new approach is applied to the spin-boson model with different sets of parameters, to investigate the convergence of the high order expansions of the TCL generator. We also discuss circumstances where the exact TCL generator becomes singular for the spin-boson model, and a model of excitation energy transfer in the Fenna-Matthews-Olson complex.
The spin-boson model is a widely used model for understanding the properties of a two-level open quantum system. Accurately describing its dynamics often requires going beyond the weak system-environment coupling approximation. However, calculating the higher-order generators of such a dynamics, with a system-environment coupling that is not too weak, has been known to be challenging, both numerically and analytically. This work presents the analytical derivation of the complete fourth-order time-convolutionless (TCL) generator for a generic spin-boson model, accurate up to 4th order in the system-environment coupling parameter, under the assumption that the environmental spectral density is an odd function of frequency. In the case of a semiconductor double-quantum-dot system, our results reveal corrections to the dynamics that may become physically significant in some parameter regimes. Furthermore, we report that the widely used second-order TCL master equation tends to overestimate the non-Markovianity of a dynamics over a large parameter regime. Within the regime of its applicability, our results provide a computational advantage over numerically exact techniques. The accuracy of the fourth-order TCL generator is rigorously benchmarked against specialized analytical calculations done for the Ohmic spectral density with Drude cutoff and against the numerically exact Hierarchical Equations of Motion technique.
The non-Markovian dynamics of an open quantum system can be rigorously derived using the Feynman–Vernon influence functional approach. Although this formalism is exact, practical numerical implementations often require compromises. The time-convolutionless (TCL) master equation offers an exact framework, yet its application typically relies on a perturbative expansion of both the time forward and time backward state propagators. Due to the significant computational effort involved—and the scarcity of analytical solutions for most open quantum systems—the fourth-order perturbative TCL generator (TCL4) has only been benchmarked on a limited range of systems and parameter spaces. Recent advancements, however, have made the computation of TCL4 faster and more accessible. In this paper, we benchmark the TCL4 master equation against numerically exact methods for the biased spin-boson model. We focus on the regime near critical bath coupling where perturbative master equations are expected to become inaccurate. Our findings reveal that the TCL4 approach is most reliable at low temperatures and more efficient than the numerical exact methods. This study aims to delineate the conditions under which the TCL4 perturbative master equation enhances the accuracy of the TCL2.
The generalized quantum master equation provides a powerful tool to describe the dynamics in quantum impurity models driven away from equilibrium. Two complementary approaches, one based on Nakajima-Zwanzig-Mori time-convolution (TC) and the other on the Tokuyama-Mori time-convolutionless (TCL) formulations provide a starting point to describe the time-evolution of the reduced density matrix. A key in both approaches is to obtain the so called "memory kernel" or "generator," going beyond second or fourth order perturbation techniques. While numerically converged techniques are available for the TC memory kernel, the canonical approach to obtain the TCL generator is based on inverting a super-operator in the full Hilbert space, which is difficult to perform and thus, nearly all applications of the TCL approach rely on a perturbative scheme of some sort. Here, the TCL generator is expressed using a reduced system propagator which can be obtained from system observables alone and requires the calculation of super-operators and their inverse in the reduced Hilbert space rather than the full one. This makes the formulation amenable to quantum impurity solvers or to diagrammatic techniques, such as the nonequilibrium Green's function. We implement the TCL approach for the resonant level model driven away from equilibrium and compare the time scales for the decay of the generator with that of the memory kernel in the TC approach. Furthermore, the effects of temperature, source-drain bias, and gate potential on the TCL/TC generators are discussed.
We explore the performance of the time-convolutionless (TCL) projection operator technique using the Fano-Anderson model as a test case. Comparing the exact TCL master equation with an expansion in powers of the strength of the system-environment coupling, we analyze the transient dynamics as well as the steady-state behavior. For a Lorentzian spectral density we demonstrate that the dimensionless expansion parameter corresponds to the ratio of the environmental correlation time to the relaxation time of the system, and we derive the convergence radius for the TCL expansion, which is seen to depend on the ratio of detuning and width of the spectral density. We further study the quantum non-Markovianity of the model based on the evolution of the Bures distance between quantum states and how it is represented by the second and fourth order of the expansion. Our results highlight both the strengths and the limitations of the TCL formalism in capturing key features of open quantum systems and, in particular, the challenges of accurately describing strongly coupled systems and non-Markovian dynamics.
The Nakajima-Zwanzig generalized master equation provides a formally exact framework to simulate quantum dynamics in condensed phases. Yet, the exact memory kernel is hard to obtain and calculations based on perturbative expansions are often employed. By using the spin-boson model as an example, we assess the convergence of high order memory kernels in the Nakajima-Zwanzig generalized master equation. The exact memory kernels are calculated by combining the hierarchical equation of motion approach and the Dyson expansion of the exact memory kernel. High order expansions of the memory kernels are obtained by extending our previous work to calculate perturbative expansions of open system quantum dynamics [M. Xu et al., J. Chem. Phys. 146, 064102 (2017)]. It is found that the high order expansions do not necessarily converge in certain parameter regimes where the exact kernel show a long memory time, especially in cases of slow bath, weak system-bath coupling, and low temperature. Effectiveness of the Padé and Landau-Zener resummation approaches is tested, and the convergence of higher order rate constants beyond Fermi's golden rule is investigated.
We attempt to modify the time-convolutionless master equation (TCL-ME) to be more resistant to breakdown. We remove the standard assumption that a portion of the generator is invertible by instead taking the Moore-Penrose inverse. We rederive the perturbative expansion using Israel and Charnes' result, and test the equation up to sixth and fifth orders on the Jaynes-Cummings and Ising models, respectively. We find that in both cases, the modified equation fails to capture the dynamics of the exact solution compared to the standard TCL due to the terms of the modified equation scaling exponentially with the dimension of the bath, and connect this failure to a loss of convergence of the perturbative expansion.