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The Journal of Chemical Physics

Convergence of high order perturbative expansions in open system quantum dynamics

Meng Xu, Linze Song, Kai Song, Qiang Shi

Published Feb 8, 2017• 25 citations
Publisher

Abstract

We propose a new method to directly calculate high order perturbative expansion terms in open system quantum dynamics. They are first written explicitly in path integral expressions. A set of differential equations are then derived by extending the hierarchical equation of motion (HEOM) approach. As two typical examples for the bosonic and fermionic baths, specific forms of the extended HEOM are obtained for the spin-boson model and the Anderson impurity model. Numerical results are then presented for these two models. General trends of the high order perturbation terms as well as the necessary orders for the perturbative expansions to converge are analyzed.

DOI
10.1063/1.4974926

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We propose a new method to directly calculate high order perturbative expansion terms in open system quantum dynamics. They are first written explicitly in path integral expressions. A set of differential equations are then derived by extending the hierarchical equation of motion (HEOM) approach. As two typical examples for the bosonic and fermionic baths, specific forms of the extended HEOM are obtained for the spin-boson model and the Anderson impurity model. Numerical results are then presented for these two models. General trends of the high order perturbation terms as well as the necessary orders for the perturbative expansions to converge are analyzed.
An extended hierarchy equation of motion (HEOM) is proposed and applied to study the dynamics of the spin-boson model. In this approach, a complete set of orthonormal functions are used to expand an arbitrary bath correlation function. As a result, a complete dynamic basis set is constructed by including the system reduced density matrix and auxiliary fields composed of these expansion functions, where the extended HEOM is derived for the time derivative of each element. The reliability of the extended HEOM is demonstrated by comparison with the stochastic Hamiltonian approach under room-temperature classical ohmic and sub-ohmic noises and the multilayer multiconfiguration time-dependent Hartree theory under zero-temperature quantum ohmic noise. Upon increasing the order in the hierarchical expansion, the result obtained from the extended HOEM systematically converges to the numerically exact answer.
The hierarchical equations of motion (HEOM) approach is one of the most powerful methods avail- able to simulate the dynamics of open quantum systems. Although the HEOM approach has been shown to be stable and efficient in many parameter regimes and physical scenarios, it is also well known that the unavoidable finite truncation of the hierarchy can lead to fundamental numeri- cal instabilities for bosonic environments. In this work, we apply recently developed techniques to analyze these issues. We use an auxiliary Fock-space picture of the hierarchy to first identify the unbalanced hierarchy-raising terms responsible for the strong transient amplification associated with the non-normal algebraic structure of the HEOM generator. We then apply a non-unitary similarity transformation that converts these terms into balanced combinations of hierarchy-raising and hierarchy-lowering terms, thereby suppressing their numerical impact. We first demonstrate the efficacy of this approach via a spin-boson model with a simple Brownian oscillator spectral den- sity and subsequently extend the analysis to a structured spectral density, showing for both cases that the transformed HEOM approach allows simulations of much larger system-bath coupling than would otherwise be possible.
We investigated applications of the hierarchical equation of motion (HEOM) method to perform high order perturbation calculations of reduced quantum dynamics for a harmonic bath with arbitrary spectral densities. Three different schemes are used to decompose the bath spectral density into analytical forms that are suitable to the HEOM treatment: (1) The multiple Lorentzian mode model that can be obtained by numerically fitting the model spectral density. (2) The combined Debye and oscillatory Debye modes model that can be constructed by fitting the corresponding classical bath correlation function. (3) A new method that uses undamped harmonic oscillator modes explicitly in the HEOM formalism. Methods to extract system-bath correlations were investigated for the above bath decomposition schemes. We also show that HEOM in the undamped harmonic oscillator modes can give detailed information on the partial Wigner transform of the total density operator. Theoretical analysis and numerical simulations of the spin-Boson dynamics and the absorption line shape of molecular dimers show that the HEOM formalism for high order perturbations can serve as an important tool in studying the quantum dissipative dynamics in the intermediate coupling regime.
We develop a quantum-classical hierarchical equations of motion (QC-HEOM) approach for simulating non-Markovian open quantum systems. The method combines the ensemble-averaged classical path reference of the quantum-classical path integral formalism with a hierarchy of auxiliary quantum influence functionals. By incorporating thermal fluctuations through an ensemble average over reference trajectories, the hierarchy is required to represent only the residual quantum memory associated with the imaginary part of the bath response function. Consequently, unlike conventional hierarchical equations of motion, QC-HEOM does not require Matsubara or Padé expansions of the thermal kernel and exhibits only weak temperature dependence of the hierarchy size. Furthermore, because thermal fluctuations are supplied through reference classical trajectories, the framework naturally extends beyond harmonic baths and enables the incorporation of anharmonic and molecular environments through externally generated trajectories. We derive the formalism and demonstrate its exactness for a harmonic bath. Applications to an asymmetric spin-boson model and the seven-site Fenna--Matthews--Olson complex illustrate the accuracy of QC-HEOM. It reproduces benchmark quasi-adiabatic path integral and hierarchical equations of motion results while requiring substantially fewer auxiliary objects, particularly at low temperatures. These results establish QC-HEOM as an efficient framework for treating residual quantum memory in quantum-classical descriptions of open-system dynamics. The separation of thermal fluctuations from residual quantum memory through the use of Wigner trajectories provides an approximate route toward hierarchical treatments of complex anharmonic environments that are inaccessible to conventional HEOM approaches.
We unite two of the most widely used approaches for strongly damped, non-Markovian open quantum dynamics, the Hierarchical Equations of Motion (HEOM) and the pseudomode method by proving two statements: First, every physical bath correlation function (BCF) that can be written as a sum of NNN exponential terms can be obtained from a physical model with NNN interacting pseudomodes which are damped in Lindblad form. Second, for every such BCF there exists a non-unitary, linear transformation which mirrors the evolution of the system-pseudomode state onto the HEOM hierarchy, and vice versa. Our proofs are constructive and we give explicit expressions for the mirror transformation as well as for the pseudomode Lindbladian corresponding to a given exponential BCF. This approach also gives insight and provides elegant derivations of the corresponding Hierarchy of stochastic Pure States (HOPS) method and its nearly-unitary version, nuHOPS. Our result opens several avenues for further optimization of non-Markovian open quantum system dynamics methods.
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.