In the previous paper [C. W. Kim and I. Franco, J. Chem. Phys. 160, 214111-1-214111-13 (2024)], we developed a theory called MQME-D, which allows us to decompose the overall energy dissipation process in open quantum system dynamics into contributions by individual components of the bath when the subsystem dynamics is governed by a Markovian quantum master equation (MQME). Here, we contrast the predictions of MQME-D against the numerically exact results obtained by combining hierarchical equations of motion (HEOM) with a recently reported protocol for monitoring the statistics of the bath. Overall, MQME-D accurately captures the contributions of specific bath components to the overall dissipation while greatly reducing the computational cost compared to exact computations using HEOM. The computations show that MQME-D exhibits errors originating from its inherent Markov approximation. We demonstrate that its accuracy can be significantly increased by incorporating non-Markovianity by exploiting time scale separations (TSS) in different components of the bath. Our work demonstrates that MQME-D combined with TSS can be reliably used to understand how energy is dissipated in realistic open quantum system dynamics.
In the previous paper [C. W. Kim and I. Franco, J. Chem. Phys. 160, 214111-1-214111-13 (2024)], we developed a theory called MQME-D, which allows us to decompose the overall energy dissipation process in open quantum system dynamics into contributions by individual components of the bath when the subsystem dynamics is governed by a Markovian quantum master equation (MQME). Here, we contrast the predictions of MQME-D against the numerically exact results obtained by combining hierarchical equations of motion (HEOM) with a recently reported protocol for monitoring the statistics of the bath. Overall, MQME-D accurately captures the contributions of specific bath components to the overall dissipation while greatly reducing the computational cost compared to exact computations using HEOM. The computations show that MQME-D exhibits errors originating from its inherent Markov approximation. We demonstrate that its accuracy can be significantly increased by incorporating non-Markovianity by exploiting time scale separations (TSS) in different components of the bath. Our work demonstrates that MQME-D combined with TSS can be reliably used to understand how energy is dissipated in realistic open quantum system dynamics.
We present a general and practical theoretical framework to investigate how energy is dissipated in open quantum system dynamics. This is performed by quantifying the contributions of individual bath components to the overall dissipation of the system. The framework is based on the Nakajima-Zwanzig projection operator technique, which allows us to express the rate of energy dissipation into a specific bath degree of freedom by using traces of operator products. The approach captures system-bath interactions to all orders, but is based on second-order perturbation theory on the off-diagonal subsystem's couplings and a Markovian description of the bath. The usefulness of our theory is demonstrated by applying it to various models of open quantum systems involving harmonic oscillators or spin baths and connecting the outcomes to existing results such as our previously reported formula derived for locally coupled harmonic baths [Kim and Franco, J. Chem. Phys. 154, 084109 (2021)]. We also prove that the dissipation calculated by our theory rigorously satisfies thermodynamic principles such as energy conservation and detailed balance. Overall, the strategy can be used to develop the theory and simulation of dissipation pathways to interpret and engineer the dynamics of open quantum systems.
Reducing computational scaling for simulating non-Markovian dissipative dynamics using artificial neural networks is both a major focus and formidable challenge in open quantum systems. To enable neural quantum states (NQSs), we encode environmental memory in dissipatons (quasiparticles with characteristic lifetimes), yielding the dissipaton-embedded quantum master equation (DQME). The resulting NQS-DQME framework achieves compact representation of many-body correlations and non-Markovian memory. Benchmarking against numerically exact hierarchical equations of motion confirms NQS-DQME maintains comparable accuracy while enhancing scalability and interpretability. This methodology opens new paths to explore non-Markovian open quantum dynamics in previously intractable systems.
Embedding non-Markovian open quantum dynamics into an enlarged Markovian space offers a powerful route to nonperturbative simulations, where the dynamics of the extended space can be governed by multiple distinct Markovian equations. We show that these distinct embeddings arise from different unravelings of Gaussian bath self-energies, generating a family of deterministic, time-local equations for the extended system. Using the Brownian-oscillator spectral density as an illustrative example, we clarify the relationships among existing approaches, including the Hierarchical Equations of Motion (HEOM) and the Lindblad--pseudomode formalism, and demonstrate how this framework enables numerically stable and efficient simulations. This work provides both a transparent theoretical foundation for embedding techniques and a flexible platform for developing new methods to simulate non-Markovian quantum dynamics.
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.
Recent advances in quantum technologies and related experiments have created a need for highly accurate, versatile, and computationally efficient simulation techniques for the dynamics of open quantum systems. Long-lived correlation effects (non-Markovianity), system-environment hybridization, and the necessity for accuracy beyond the Born-Markov approximation form particular challenges. Approaches to meet these challenges have been introduced, originating from different fields, such as hierarchical equations of motion, Lindblad-pseudomode formulas, chain-mapping approaches, quantum Brownian motion master equations, stochastic unravelings, and refined quantum master equations. This diversity, while indicative of the field's relevance, has inadvertently led to a fragmentation that hinders cohesive advances and their effective cross-community application to current problems for complex systems. How are different approaches related to each other? What are their strengths and limitations? Here we give a systematic overview and concise discussion addressing these questions. We make use of a unified framework which very conveniently allows to link different schemes and, this way, may also catalyze further progress. In line with the state of the art, this framework is formulated not in a fully reduced space of the system but in an extended state space which in a minimal fashion includes effective reservoir modes. This in turn offers a comprehensive understanding of existing methods, elucidating their physical interpretations, interconnections, and applicability.
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.