Estimating memory time within the frameworks of generalized quantum master equation and transfer tensor methods
Simulating long-time nonadiabatic dynamics in condensed-phase systems is computationally demanding due to the inherent non-Markovianity of the electronic reduced density matrix evolution. While the generalized quantum master equation (GQME) and transfer tensor method (TTM) allow for the reconstruction of long-time dynamics from short-time projection-free inputs, their accuracy hinges on the rigorous estimation of the memory time, a parameter often determined by heuristic trial-and-error. In this work, we establish a comprehensive framework for estimating memory time and benchmarking propagation accuracy using semiclassical and numerical exact inputs on both standard spin-boson models and general multistate harmonic models. We develop an error estimation scheme that reveals a characteristic three-stage decay pattern in the non-Markovian propagation error: an initial transient drop, an exponential decay, and a saturation plateau. This estimator serves as a critical diagnostic tool for GQME and TTM, successfully distinguishing between converged predictions and reliability failures in complex systems, such as the carotenoid-porphyrin-fullerene triad. These findings provide a robust, quantitative protocol for validating memory-kernel-based simulations of nonadiabatic dynamics.
Authors
- Hao Zeng (ORCID: https://orcid.org/0009-0001-8584-8718)
- Xiang Sun (ORCID: https://orcid.org/0000-0002-2846-8532)
Institutions
- New York University Shanghai (CN)
- New York University (US)
- East China Normal University (CN)
Publication Details
- Journal
- The Journal of Chemical Physics
- Published
- 2026-06-09
- DOI
- https://doi.org/10.1063/5.0325277
- Primary Topic
- Spectroscopy and Quantum Chemical Studies
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Natural Science Foundation of China