Coarse-Grained Nonadiabatic Dynamics in Disordered Condensed Phases.
5 affiliations
- 1Division of Arts and Sciences, NYU Shanghai, 567 West Yangsi Road, Shanghai200124, China.
- 2Department of Chemistry, New York University, New York, New York10003, United States.
- 3NYU-ECNU Center for Computational Chemistry at NYU Shanghai , 3663 Zhongshan Road North, Shanghai200062, China.
- 4School of Chemistry and Molecular Engineering, East China Normal University, Shanghai200062, China.
- 5School of Chemistry and Materials Science, Nanjing Normal University, Nanjing210000, China.
Abstract
The mechanisms underlying critical energy-gap fluctuations and nonadiabatic dynamics in disordered condensed phases remain elusive, and their accurate simulation poses a challenge due to the inherent complexity of these systems. In this study, we make the first attempt to leverage highly efficient coarse-grained (CG) models to investigate these fundamental mechanisms. Employing a rigorous bottom-up parameterization approach, we construct CG models for two prototypical systems: a carotenoid-porphyrin-fullerene triad in tetrahydrofuran and a perylene diimide dimer in acetonitrile. Using nonadiabatic semiclassical mapping dynamics, we evaluate a hierarchy of representations spanning fully atomistic explicit-molecule simulations, intermediate CG resolutions, and highly reduced multistate harmonic (MSH) models to assess their impact on energy-gap fluctuations and nonadiabatic properties. A distinct advantage of these explicit-molecule simulations is their ability to yield time-dependent radial distribution functions, revealing the detailed molecular picture of localized solvent rearrangement upon photoinduced charge transfer. Our results confirm that with appropriate coarse-graining of the solvent and solute, the resulting CG models faithfully preserve the structural responses, pairwise reorganization energies, and electronic population dynamics of the atomistic benchmark. Conversely, aggressive 2-heavy-atom solute mapping severely distorts local nonbonded environments. Importantly, MSH models parameterized from structurally valid CG simulations successfully reproduce explicit-molecule dynamics while discarding tens of thousands of degrees of freedom. This work provides a new, highly efficient theoretical foundation for scaling nonadiabatic dynamics simulations to larger and more complex condensed-phase systems.
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BibTeX
@article{song2026coarsegrained,
title = {{Coarse-Grained Nonadiabatic Dynamics in Disordered Condensed Phases.}},
author = {Zailing Song and Zengkui Liu and Fei Xia and Yuwei Zhang and Xiang Sun},
journal = {Journal of chemical theory and computation},
year = {2026},
month = sep,
doi = {10.1021/acs.jctc.6c01363},
url = {https://europepmc.org/article/MED/42917464},
note = {CC BY},
}
RIS
TY - JOUR
TI - Coarse-Grained Nonadiabatic Dynamics in Disordered Condensed Phases.
AU - Zailing Song
AU - Zengkui Liu
AU - Fei Xia
AU - Yuwei Zhang
AU - Xiang Sun
PY - 2026
DA - 2026/09/01
JO - Journal of chemical theory and computation
DO - 10.1021/acs.jctc.6c01363
UR - https://europepmc.org/article/MED/42917464
AB - The mechanisms underlying critical energy-gap fluctuations and nonadiabatic dynamics in disordered condensed phases remain elusive, and their accurate simulation poses a challenge due to the inherent complexity of these systems. In this study, we make the first attempt to leverage highly efficient coarse-grained (CG) models to investigate these fundamental mechanisms. Employing a rigorous bottom-up parameterization approach, we construct CG models for two prototypical systems: a carotenoid-porphyrin-fullerene triad in tetrahydrofuran and a perylene diimide dimer in acetonitrile. Using nonadiabatic semiclassical mapping dynamics, we evaluate a hierarchy of representations spanning fully atomistic explicit-molecule simulations, intermediate CG resolutions, and highly reduced multistate harmonic (MSH) models to assess their impact on energy-gap fluctuations and nonadiabatic properties. A distinct advantage of these explicit-molecule simulations is their ability to yield time-dependent radial distribution functions, revealing the detailed molecular picture of localized solvent rearrangement upon photoinduced charge transfer. Our results confirm that with appropriate coarse-graining of the solvent and solute, the resulting CG models faithfully preserve the structural responses, pairwise reorganization energies, and electronic population dynamics of the atomistic benchmark. Conversely, aggressive 2-heavy-atom solute mapping severely distorts local nonbonded environments. Importantly, MSH models parameterized from structurally valid CG simulations successfully reproduce explicit-molecule dynamics while discarding tens of thousands of degrees of freedom. This work provides a new, highly efficient theoretical foundation for scaling nonadiabatic dynamics simulations to larger and more complex condensed-phase systems.
SN - 1549-9618
SN - 1549-9626
ER -