Collective vibrational strong coupling triggers dissociation reaction by overcoming energy threshold
6 affiliations
- 1Department of Chemistry, Shanghai Key Laboratory of Electrochemical and Thermochemical Conversion for Resources Recycling, State Key Laboratory of Porous Materials for Separation and Conversion
- 2Fudan University
- 3Department of Physics
- 4Dalian University of Technology
- 5State Key Laboratory of Chemical Reaction Dynamics
- 6Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Abstract
Ground-state reactions under vibrational strong coupling (VSC) have emerged as one of the central topics in polariton chemistry, yet how the energy redistribution under collective VSC translates into chemical reactivity remains an open question. Here we investigate vibrational predissociation in dilute ensembles of water trimers coupled to an optical cavity using full-dimensional cavity quasi-classical trajectory (cav-QCT) simulations with ab initio-quality potential-energy and dipole-moment surfaces. We demonstrate that collective VSC directly induces an otherwise energetically forbidden dissociation of the water trimer through cavity-mediated intermolecular VET. Remarkably, the enhancement of reactivity remains observable with increasing ensemble size despite reduced effective single-molecule light–matter coupling strength. Trajectory analyses identify collective energy transfer as the microscopic mechanism and reveal largely consistent quantum-state distributions of the reaction products. These findings establish a microscopic link between collective polaritonic energy transport and chemical reactivity, and suggest collective VSC as a route toward simultaneously manipulating reactivity and preserving product-state selectivity.
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BibTeX
@misc{ding2026collective,
title = {{Collective vibrational strong coupling triggers dissociation reaction by overcoming energy threshold}},
author = {Mingliang Ding and Ruitao Ma and Dianfang Chen and Yongchang Han and Dong H. Zhang and Qi Yu},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15009470/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009470/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Collective vibrational strong coupling triggers dissociation reaction by overcoming energy threshold
AU - Mingliang Ding
AU - Ruitao Ma
AU - Dianfang Chen
AU - Yongchang Han
AU - Dong H. Zhang
AU - Qi Yu
PY - 2026
DA - 2026/09/25
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009470/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009470/v1
AB - Ground-state reactions under vibrational strong coupling (VSC) have emerged as one of the central topics in polariton chemistry, yet how the energy redistribution under collective VSC translates into chemical reactivity remains an open question. Here we investigate vibrational predissociation in dilute ensembles of water trimers coupled to an optical cavity using full-dimensional cavity quasi-classical trajectory (cav-QCT) simulations with ab initio-quality potential-energy and dipole-moment surfaces. We demonstrate that collective VSC directly induces an otherwise energetically forbidden dissociation of the water trimer through cavity-mediated intermolecular VET. Remarkably, the enhancement of reactivity remains observable with increasing ensemble size despite reduced effective single-molecule light–matter coupling strength. Trajectory analyses identify collective energy transfer as the microscopic mechanism and reveal largely consistent quantum-state distributions of the reaction products. These findings establish a microscopic link between collective polaritonic energy transport and chemical reactivity, and suggest collective VSC as a route toward simultaneously manipulating reactivity and preserving product-state selectivity.
ER -