Collective vibrational strong coupling triggers dissociation reaction by overcoming energy threshold
Year: 2026
Type: preprint
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.
Source: ChemRxiv
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
Awards: G2241535341, G8896426441
OpenAlex ID: W7214405357