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

Institutions

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

Controls
|||
ALL TIME
JAN
FEB
MAR
APR
MAY
JUN
JUL
AUG
SEP
OCT
article

Estimating memory time within the frameworks of generalized quantum master equation and transfer tensor methods

Hao Zeng, Xiang Sun
The Journal of Chemical Physics
Spectroscopy and Quantum Chemical Studies
article

Estimating memory time within the frameworks of generalized quantum master equation and transfer tensor methods

Hao Zeng, Xiang Sun
article en

Abstract

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.

The Journal of Chemical PhysicsVol. 164(22)
New York University Shanghai (CN), New York University (US), East China Normal University (CN)
National Natural Science Foundation of China
Openalex Percentile: Top 6%
Spectroscopy and Quantum Chemical Studies
AI Navigator

Ask Laika to Summarize, Analyze, and Connect papers live on the map.

Summarize Papers & Methodologies

Extract key findings, datasets, and comparative methods across publications.

Benchmark Rankings & Visual Analytics

Rank top research institutions, authors, funders, topics, and journals by Field-Weighted Citation Impact (FWCI) and paper volume with instant charts.

Connect Distant Disciplines

Bridge topological clusters on the map to find hidden collaborative intersections.

Estimating memory time within the frameworks of generalized quantum master equation and transfer tensor methods — Hao Zeng, Xiang Sun · The Journal of Chemical Physics (2026) | TGRS Research Map | TGRS