Nonadiabatic Semiclassical Polariton Dynamics: Excited State Proton Transfer of Aminopropenal
Abstract
The interplay between strong light-matter coupling and nonadiabatic molecular dynamics provides a promising route to control chemical reactivity. Here, we develop a framework for simulating polaritonic chemistry with on-the-fly semiclassical nonadiabatic molecular dynamics, employing the linearized semiclassical initial value representation. With this approach, we simulate the nonadiabatic molecular dynamics under strong light-matter coupling, presenting results for excited state proton transfer of aminopropenal. Light-matter interactions are described using a Jaynes-Cummings Hamiltonian formulated in the adiabatic electronic basis, where the electronic energies, transition moments, and nuclear forces are evaluated on the fly. We characterize how light-matter coupling reshapes reaction pathways and redistributes photonic and electronic character of individual states along the trajectory, finding that photonic character of the lower polaritonic state decreases in time as the molecular geometry relaxes, demonstrating that the cavity effect is strongest during the initial dynamics. We find that for aminopropenal, the main effect of cavity coupling on the dynamics is not altering the proton transfer barrier, but instead altering the excited-state relaxation network by introducing an additional polaritonic state with favorable proton transfer energetics. By analyzing the population transfer between excited states, we find that cavity coupling leads to population being temporarily redirected into this intermediate state, delaying population relaxation to a high-barrier excited state. This change in timing results in a higher fraction of trajectories undergoing proton transfer. Our new computational protocol that connects on-the-fly semiclassical nonadiabatic dynamics and polaritonic frameworks provides trajectory-resolved insight into how cavity coupling modifies nonadiabatic population transfer and proton-transfer dynamics.
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BibTeX
@misc{majumdar2026nonadiabatic,
title = {{Nonadiabatic Semiclassical Polariton Dynamics: Excited State Proton Transfer of Aminopropenal}},
author = {Sourav Majumdar and Christopher A. Myers and Darwin Martinez and Christine M. Isborn},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010520/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010520/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Nonadiabatic Semiclassical Polariton Dynamics: Excited State Proton Transfer of Aminopropenal
AU - Sourav Majumdar
AU - Christopher A. Myers
AU - Darwin Martinez
AU - Christine M. Isborn
PY - 2026
DA - 2026/10/15
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010520/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010520/v1
AB - The interplay between strong light-matter coupling and nonadiabatic molecular dynamics provides a promising route to control chemical reactivity. Here, we develop a framework for simulating polaritonic chemistry with on-the-fly semiclassical nonadiabatic molecular dynamics, employing the linearized semiclassical initial value representation. With this approach, we simulate the nonadiabatic molecular dynamics under strong light-matter coupling, presenting results for excited state proton transfer of aminopropenal. Light-matter interactions are described using a Jaynes-Cummings Hamiltonian formulated in the adiabatic electronic basis, where the electronic energies, transition moments, and nuclear forces are evaluated on the fly. We characterize how light-matter coupling reshapes reaction pathways and redistributes photonic and electronic character of individual states along the trajectory, finding that photonic character of the lower polaritonic state decreases in time as the molecular geometry relaxes, demonstrating that the cavity effect is strongest during the initial dynamics. We find that for aminopropenal, the main effect of cavity coupling on the dynamics is not altering the proton transfer barrier, but instead altering the excited-state relaxation network by introducing an additional polaritonic state with favorable proton transfer energetics. By analyzing the population transfer between excited states, we find that cavity coupling leads to population being temporarily redirected into this intermediate state, delaying population relaxation to a high-barrier excited state. This change in timing results in a higher fraction of trajectories undergoing proton transfer. Our new computational protocol that connects on-the-fly semiclassical nonadiabatic dynamics and polaritonic frameworks provides trajectory-resolved insight into how cavity coupling modifies nonadiabatic population transfer and proton-transfer dynamics.
ER -