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arXiv:2606.30569

Revisiting crossed-correlated baths in open quantum systems simulated by HEOM or T-TEDOPA

Brieuc Le Dé, Etienne Mangaud, Alex W. Chin, Michèle Desouter-Lecomte

quant-phphysics.chem-phSubmitted Jun 29, 2026• Announced Jun 30, 2026
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Abstract

Excited-state dynamics of open quantum systems is analyzed by the hierarchical equations of motion (HEOM) or the thermalized time-evolving density operator with orthogonal polynomials algorithm (T-TEDOPA) method when a discrete $ab$ $initio$ linear vibronic model is parametrized by continuous temperature-dependent spectral densities leading to crossed correlation functions, i.e. correlated fluctuations of the energy gap collective modes. We focus on a conical intersection involving two collective modes tuning the energy of each excited state and we revisit the transformation of the initial correlated tuning baths to de-correlated shared baths in order to reduce the computational resources. While a completely frequency-dependent transformation poses problems for HEOM, we find that in some particular cases, an optimal approximate frequency-independent transformation may be derived. On the contrary, T-TEDOPA is very efficient and allows to use this frequency-dependent transformation at the price of managing long-range couplings in the tensor chain. An illustrative application is shown by using the linear vibronic coupling model of a planar symmetrical (phenylethynyl)benzene dimer.

Comments
30 pages, 12 figures

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Excited-state dynamics of open quantum systems is analyzed by the hierarchical equations of motion (HEOM) or the thermalized time-evolving density operator with orthogonal polynomials algorithm (T-TEDOPA) method when a discrete ababab initioinitioinitio linear vibronic model is parametrized by continuous temperature-dependent spectral densities leading to crossed correlation functions, i.e. correlated fluctuations of the energy gap collective modes. We focus on a conical intersection involving two collective modes tuning the energy of each excited state and we revisit the transformation of the initial correlated tuning baths to de-correlated shared baths in order to reduce the computational resources. While a completely frequency-dependent transformation poses problems for HEOM, we find that in some particular cases, an optimal approximate frequency-independent transformation may be derived. On the contrary, T-TEDOPA is very efficient and allows to use this frequency-dependent transformation at the price of managing long-range couplings in the tensor chain. An illustrative application is shown by using the linear vibronic coupling model of a planar symmetrical (phenylethynyl)benzene dimer.
In non-perturbative non-Markovian open quantum systems, reaching either low temperatures with the hierarchical equations of motion (HEOM) or high temperatures with the Thermalized Time Evolving Density Operator with Orthogonal Polynomials Algorithm (T-TEDOPA) formalism in Hilbert space remains challenging. We compare different ways of modeling the environment. Sampling the Fourier transform of the bath correlation function, also called temperature dependent spectral density, proves to be very effective. T-TEDOPA [Tamascelli et al., Phys. Rev. Lett. 123, 090402 (2019)] uses a linear chain of oscillators with positive and negative frequencies, while HEOM is based on the complex poles of an optimized rational decomposition of the temperature dependent spectral density [Xu et al., Phys. Rev. Lett. 129, 230601 (2022)]. Resorting to the poles of the temperature independent spectral density and of the Bose function separately is an alternative when the problem due to the huge number of Bose poles at low temperatures is circumvented. Two examples illustrate the effectiveness of the HEOM and T-TEDOPA approaches: a benchmark pure dephasing case and a two-bath model simulating the dynamics of excited electronic states coupled through a conical intersection. We show the efficiency of T-TEDOPA to simulate dynamics at a finite temperature by using either continuous spectral densities or only all the intramolecular oscillators of a linear vibronic model calibrated from ab initio data of a phenylene ethynylene dimer.
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.
Classical non-perturbative simulations of open quantum systems' dynamics face several scalability problems, namely, exponential scaling of the computational effort as a function of either the time length of the simulation or the size of the open system. In this work, we propose the use of the Time Evolving Density operator with Orthogonal Polynomials Algorithm (TEDOPA) on a quantum computer, which we term as Quantum TEDOPA (Q-TEDOPA), to simulate non-perturbative dynamics of open quantum systems linearly coupled to a bosonic environment (continuous phonon bath). By performing a change of basis of the Hamiltonian, the TEDOPA yields a chain of harmonic oscillators with only local nearest-neighbour interactions, making this algorithm suitable for implementation on quantum devices with limited qubit connectivity such as superconducting quantum processors. We analyse in detail the implementation of the TEDOPA on a quantum device and show that exponential scalings of computational resources can potentially be avoided for time-evolution simulations of the systems considered in this work. We applied the proposed method to the simulation of the exciton transport between two light-harvesting molecules in the regime of moderate coupling strength to a non-Markovian harmonic oscillator environment on an IBMQ device. Applications of the Q-TEDOPA span problems which can not be solved by perturbation techniques belonging to different areas, such as the dynamics of quantum biological systems and strongly correlated condensed matter systems.
An open quantum system refers to a system that is further coupled to a bath system consisting of surrounding radiation fields, atoms, molecules, or proteins. The bath system is typically modeled by an infinite number of harmonic oscillators. This system-bath model can describe the time-irreversible dynamics through which the system evolves toward a thermal equilibrium state at finite temperature. In nuclear magnetic resonance and atomic spectroscopy, dynamics can be studied easily by using simple quantum master equations under the assumption that the system-bath interaction is weak (perturbative approximation) and the bath fluctuations are very fast (Markovian approximation). However, such approximations cannot be applied in chemical physics and biochemical physics problems, where environmental materials are complex and strongly coupled with environments. The hierarchical equations of motion (HEOM) can describe the numerically "exact" dynamics of a reduced system under nonperturbative and non-Markovian system-bath interactions, which has been verified on the basis of exact analytical solutions (non-Markovian tests) with any desired numerical accuracy. The HEOM theory has been used to treat systems of practical interest, in particular, to account for various linear and nonlinear spectra in molecular and solid state materials, to evaluate charge and exciton transfer rates in biological systems, to simulate resonant tunneling and quantum ratchet processes in nanodevices, and to explore quantum entanglement states in quantum information theories. This article presents an overview of the HEOM theory, focusing on its theoretical background and applications, to help further the development of the study of open quantum dynamics.
We develop a quasiparticle approach to capture the dynamics of open quantum systems coupled to bosonic thermal baths of arbitrary complexity based on the Hierarchical Equations of Motion (HEOM). This is done by generalizing the HEOM dynamics and mapping it into that of the system in interaction with a few bosonic fictitious quasiparticles that we call bexcitons. Bexcitons arise from a decomposition of the bath correlation function into discrete features. Specifically, bexciton creation and annihilation couple the auxiliary density matrices in the HEOM. The approach provides a systematic strategy to construct exact quantum master equations that include the system-bath coupling to all orders even for non-Markovian environments. Specifically, by introducing different metrics and representations for the bexcitons it is possible to straightforwardly generate different variants of the HEOM, demonstrating that all these variants share a common underlying quasiparticle picture. Bexcitonic properties, while unphysical, offer a coarse-grained view of the correlated system-bath dynamics and its numerical convergence. For instance, we use it to analyze the instability of the HEOM when the bath is composed of underdamped oscillators and show that it leads to the creation of highly excited bexcitons. The bexcitonic picture can also be used to develop more efficient approaches to propagate the HEOM. As an example, we use the particle-like nature of the bexcitons to introduce mode-combination of bexcitons in both number and coordinate representation that uses the multi-configuration time-dependent Hartree to efficiently propagate the HEOM dynamics.
The hierarchical equations of motion (HEOM) method has recently been widely applied to many problems of quantum dynamics in condensed phase. It is now well known that the auxiliary density operators (ADOs) in the HEOM formalism contain system-bath correlations that are important in calculating various dynamical properties, yet quantitative relations to explicitly calculate such correlations from the ADOs are still scarce. This paper extends a previous study [Q. Shi et al., J. Chem. Phys. 130, 164518 (2009)] in investigating the physical meaning of ADOs to general spectral densities and lower temperature cases. Using the path-integral technique, we derive exact relations between the expectation values of the collective bath coordinate and the ADOs, which could be very useful in investigating the correlated system-bath dynamics directly with the HEOM formalism. Numerical examples concerning the evolution of the expectation values of the collective bath coordinate are also presented.