A system with many energy states coupled to a harmonic oscillator bath is considered. To study quantum non-Markovian system-bath dynamics numerically rigorously and nonperturbatively, we developed a computer code for the reduced hierarchy equations of motion (HEOM) for a graphics processor unit (GPU) that can treat the system as large as 4096 energy states. The code employs a Padé spectrum decomposition (PSD) for a construction of HEOM and the exponential integrators. Dynamics of a quantum spin glass system are studied by calculating the free induction decay signal for the cases of 3 × 2 to 3 × 4 triangular lattices with antiferromagnetic interactions. We found that spins relax faster at lower temperature due to transitions through a quantum coherent state, as represented by the off-diagonal elements of the reduced density matrix, while it has been known that the spins relax slower due to suppression of thermal activation in a classical case. The decay of the spins are qualitatively similar regardless of the lattice sizes. The pathway of spin relaxation is analyzed under a sudden temperature drop condition. The Compute Unified Device Architecture (CUDA) based source code used in the present calculations is provided as Supporting Information .
A system with many energy states coupled to a harmonic oscillator bath is considered. To study quantum non-Markovian system-bath dynamics numerically rigorously and nonperturbatively, we developed a computer code for the reduced hierarchy equations of motion (HEOM) for a graphics processor unit (GPU) that can treat the system as large as 4096 energy states. The code employs a Padé spectrum decomposition (PSD) for a construction of HEOM and the exponential integrators. Dynamics of a quantum spin glass system are studied by calculating the free induction decay signal for the cases of 3 × 2 to 3 × 4 triangular lattices with antiferromagnetic interactions. We found that spins relax faster at lower temperature due to transitions through a quantum coherent state, as represented by the off-diagonal elements of the reduced density matrix, while it has been known that the spins relax slower due to suppression of thermal activation in a classical case. The decay of the spins are qualitatively similar regardless of the lattice sizes. The pathway of spin relaxation is analyzed under a sudden temperature drop condition. The Compute Unified Device Architecture (CUDA) based source code used in the present calculations is provided as Supporting Information .
Building upon our previous implementation for the hydrogen atom [Y. Zhang and Y. Tanimura, J. Chem. Phys. 163, 184108 (2025)], we have developed source code for atomic orbital-hierarchical equations of motion (AO-HEOM), a quantum mechanical framework based on HEOM formulated within an AO basis. This method enables numerically "exact" simulations of atomic systems coupled to three independent thermal baths, under both isotropic and anisotropic conditions, while preserving rotational symmetry. AO-HEOM rigorously accounts for system-bath entanglement, which is critical for describing the quantum nature of environmental interactions. Incorporating spatial bath degrees of freedom significantly increases the computational cost in the HEOM formalism because of the proliferation of electronic states at high temperatures and the inclusion of Matsubara frequency terms at low temperatures. To address this challenge, we developed a graphics processing unit-accelerated implementation. As a demonstration, we computed the emission spectra of He I and He II atoms. The source code is broadly applicable to atomic systems and enables detailed analysis of electronic transitions in thermal environments.
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 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.
Abstract One of the most intensively studied problems in the field of open quantum systems is the spin-boson model. In this paper, we consider an extension of the spin-boson model with non-linear coupling. We solve the entanglement dynamics of two independent spins quadratically coupled to a bath of harmonic oscillators, using numerically ”exact” approach of hierarchical equations of motion (HEOM). Without Markovian approximation, generalized influence functional formulation by Hu et.al is used to describe the environmental effect of noisy quadratic bath in high-temperature regime. Wotters concurrence is then applied to numerically solved reduced density matrix to visualize the entanglement dynamics. By adjusting the environmental parameters, we vary the degree of non-markovianity and found the elongated time of entanglement.
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.
For a system strongly coupled to a heat bath, the quantum coherence of the system and the heat bath plays an important role in the system dynamics. This is particularly true in the case of non-Markovian noise. We rigorously investigate the influence of system-bath coherence by deriving the reduced hierarchal equations of motion (HEOM), not only in real time, but also in imaginary time, which represents an inverse temperature. It is shown that the HEOM in real time obtained when we include the system-bath coherence of the initial thermal equilibrium state possess the same form as those obtained from a factorized initial state. We find that the difference in behavior of systems treated in these two manners results from the difference in initial conditions of the HEOM elements, which are defined in path integral form. We also derive HEOM along the imaginary time path to obtain the thermal equilibrium state of a system strongly coupled to a non-Markovian bath. Then, we show that the steady state hierarchy elements calculated from the real-time HEOM can be expressed in terms of the hierarchy elements calculated from the imaginary-time HEOM. Moreover, we find that the imaginary-time HEOM allow us to evaluate a number of thermodynamic variables, including the free energy, entropy, internal energy, heat capacity, and susceptibility. The expectation values of the system energy and system-bath interaction energy in the thermal equilibrium state are also evaluated.