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Journal of Chemical Theory and Computation

Accurate Two-Time Correlation from a Pseudomode-Based Variational Approach with the Multiple Davydov D1 Density Operator

Yiying Yan, Zhiguo LÜ, Yuguo Su, JunYan Luo, Yang Zhao

Published Oct 16, 2026• 0 citations
Publisher

Abstract

The pseudomode framework provides an efficient description of open quantum systems in non-Markovian and nonperturbative coupling regimes by utilizing simple Markovian Lindblad master equations that incorporate a set of damped bosonic pseudomodes. Developing an efficient numerical scheme to solve these equations accurately is highly desirable. In this work, we propose a modified multiple Davydov D1 density operator ansatz and combine it with the Dirac-Frenkel time-dependent variational principle to simulate the dynamics governed by these master equations. We apply this variational method to the spin-boson model, both with and without a periodic external driving field, and compute both single- and two-time expectation values in non-Markovian, strong-coupling regimes. The accuracy of our variational approach is validated by comparing its predictions with results obtained from the small matrix path integral method. We demonstrate that the variational and path-integral approaches are in excellent agreement for both single- and two-time expectations across nondriven and driven cases, spanning both low- and high-temperature regimes. Our results establish the reliability and broad applicability of the pseudomode-based variational approach for calculating two-time correlation functions in open quantum systems.

DOI
10.1021/acs.jctc.6c01283

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The pseudomode framework provides an efficient description of open quantum systems in non-Markovian and nonperturbative coupling regimes by utilizing simple Markovian Lindblad master equations that incorporate a set of damped bosonic pseudomodes. Developing an efficient numerical scheme to solve these equations accurately is highly desirable. In this work, we propose a modified multiple Davydov D1 density operator ansatz and combine it with the Dirac-Frenkel time-dependent variational principle to simulate the dynamics governed by these master equations. We apply this variational method to the spin-boson model, both with and without a periodic external driving field, and compute both single- and two-time expectation values in non-Markovian, strong-coupling regimes. The accuracy of our variational approach is validated by comparing its predictions with results obtained from the small matrix path integral method. We demonstrate that the variational and path-integral approaches are in excellent agreement for both single- and two-time expectations across nondriven and driven cases, spanning both low- and high-temperature regimes. Our results establish the reliability and broad applicability of the pseudomode-based variational approach for calculating two-time correlation functions in open quantum systems.
Lindblad master equations describing driven quantum systems coupled to multiple bosonic modes are central to modeling cavity quantum electrodynamics and pseudomode models. In this work, we employ the density-operator-based Dirac-Frenkel time-dependent variational principle combined with the multiple Davydov D2Ansatz to provide optimal solutions for Lindblad master equations in both multimode and driven scenarios. Our approach is benchmarked against numerically "exact" methods in two representative models. The first describes a driven qubit subject to spontaneous emission and coupled to a lossy cavity, while the second corresponds to the pseudomode Lindblad master equation derived from the driven spin-boson model, incorporating seven discrete pseudomodes. The proposed variational approach achieves excellent agreement with numerically "exact" results. Furthermore, we analyze the accuracy of the variational solutions using an error metric based on the Frobenius norm, confirming their reliability. Overall, the present method offers an accurate and computationally efficient framework for simulating Lindblad master equations in complex open quantum systems.
ABSTRACT Markovian pseudomode models are shown to accurately describe non‐Markovian and non‐perturbative reduced dynamics and multi‐time correlation functions under certain constraints. However, it is challenging to solve the Lindblad master equation for such models when a number of pseudomodes are involved. A variational approach based on multiple Davydov states is used to solve the master equation of pseudomode models for the multi‐mode Jaynes–Cummings (JC) model, and the spin‐boson system across four distinct configurations, enabling computation of the two‐time correlation function that incorporates bath phonon occupation dynamics. In parallel, calculations of the unitary evolution of full Hamiltonians are chosen as benchmark references. Benchmark comparisons demonstrate that the variational approach for Markovian pseudomode models successfully predicts both the single‐time and two‐time expectations within the multi‐mode JC model. In contrast, in the spin‐boson model, the variational simulations for the pseudomode system and the full Hamiltonian yield inconsistent bath occupation numbers in a non‐perturbative strong coupling regime despite that these two kinds of simulations predict almost identical reduced dynamics, resulting from a fitting artefact in the pseudomode model. Our findings offer insights into the applicability of the non‐unitary variational approach on the simulation of two‐time correlation functions within the pseudomode framework.
The Dirac-Frenkel time-dependent variational approach with Davydov Ansätze is a sophisticated, yet efficient technique to obtain an accurate solution to many-body Schrödinger equations for energy and charge transfer dynamics in molecular aggregates and light-harvesting complexes. We extend this variational approach to finite temperature dynamics of the spin-boson model by adopting a Monte Carlo importance sampling method. In order to demonstrate the applicability of this approach, we compare calculated real-time quantum dynamics of the spin-boson model with that from numerically exact iterative quasiadiabatic propagator path integral (QUAPI) technique. The comparison shows that our variational approach with the single Davydov Ansätze is in excellent agreement with the QUAPI method at high temperatures, while the two differ at low temperatures. Accuracy in dynamics calculations employing a multitude of Davydov trial states is found to improve substantially over the single Davydov Ansatz, especially at low temperatures. At a moderate computational cost, our variational approach with the multiple Davydov Ansatz is shown to provide accurate spin-boson dynamics over a wide range of temperatures and bath spectral densities.
The pseudomode model effectively captures the nonperturbative dynamics of open quantum systems with significantly reduced degrees of freedom. However, it is limited by the exponential growth of the Hilbert space dimension. To overcome the computational challenges, we propose a novel method that combines the multiple Davydov Ansatz with the Choi-Jamiolkowski isomorphism. Within this framework, the Lindblad equation is transformed into the non-Hermitian Schrödinger equation in a double Hilbert space, with its dynamics determined using the time-dependent variational principle. Three cases are calculated to demonstrate the effectiveness of the proposed method. We first discuss how the Davydov Ansatz works for the model with a single pseudomode. Extending the method to multiple pseudomodes, we show that the Ansatz effectively circumvents the exponential growth of the Hilbert space. Additionally, the method is also capable of addressing potential intersections that emerge in multibath scenarios. This approach offers potential applicability to various types of pseudomode models and other dissipative systems, providing a promising tool for the studies of open quantum dynamics.
We outline a non-perturbative approach for simulating the behavior of open quantum systems interacting with a bosonic environment defined by a generalized spectral density function. The method is based on replacing the environment by a set of damped harmonic oscillators - the pseudomodes - thereby forming an enlarged open system whose dynamics is governed by a Markovian master equation. Each pseudomode is connected to one of the poles of the spectral density when analytically continued to the lower-half complex frequency plane. Here, we extend previous results to a completely generic class of open system models, and discuss how our framework can be used as a powerful and versatile tool for analyzing non-Markovian open system dynamics. The effectiveness of the method is demonstrated on the spin-boson model by accurately benchmarking its predictions against numerically exact results.
The dynamics of a coupled electron–boson system is investigated by employing a multitude of the Davydov D 1 trial states, also known as the multi-D 1 Ansatz, and a second trial state based on a superposition of the time-dependent generalized coherent state (GCS Ansatz ). The two Ansätze are applied to study population dynamics in the spin-boson model and the Holstein molecular crystal model, and a detailed comparison with numerically exact results obtained by the (multilayer) multiconfiguration time-dependent Hartree method and the hierarchy equations of motion approach is drawn. It is found that the two methodologies proposed here have significantly improved over that with the single D 1 Ansatz, yielding quantitatively accurate results even in the critical cases of large energy biases and large transfer integrals. The two methodologies provide new effective tools for accurate, efficient simulation of many-body quantum dynamics thanks to a relatively small number of parameters which characterize the electron–nuclear wave functions. The wave-function-based approaches are capable of tracking explicitly detailed bosonic dynamics, which is absent by construct in approaches based on the reduced density matrix. The efficiency and flexibility of our methods are also advantages as compared with numerically exact approaches such as QUAPI and HEOM, especially at low temperatures and in the strong coupling regime.