Competing pathways in polaritonic chemistry and general harmonic environments
Abstract
Recent experiments suggest that strong light-matter coupling between molecules and cavity modes can significantly modify chemical reaction rates and yields. Despite multiple proposed mechanisms, a clear microscopic understanding of how vibrational strong coupling alters reaction kinetics remains incomplete. Here, we employ a general quantum-dynamical framework for analyzing competing reaction pathways in polaritonic chemistry by considering reaction coordinates with multiple relevant transition frequencies and general harmonic environments. We extend on a tensor-network formulation of the hierarchical equations of motion (HEOM) method to compute probability currents between vibrational states, leveraging a concise formulation for effective spectral densities and a controlled compression of Markovian bath modes into system-level jump operators. This allows us to decompose the resulting state-to-state probability currents, revealing how cavity-induced changes in individual transitions propagate through multistep reaction networks. We find that these local modifications can alter kinetic bottlenecks and selectively redistribute reaction flux between competing pathways, changing branching ratios under irreversible conditions without substantially affecting the equilibrium yield in the reversible regime. Finally, for coupled reaction-coordinate, spectator-mode, and cavity environments, we find structured, asymmetric rate profiles arising from interference between hybridized decay channels. Together, these results provide a mechanistic framework for understanding pathway-specific chemical reactivity under vibrational strong coupling.
Related
- Molecular Precursor Chemistry Shapes Early-Stage Reaction Pathways in Nitrogen-Doped Carbon Nanotube Synthesis
- Active Phase and Amplitude Modulation in Perovskite Polaritonic Waveguides
- Polaritonic self-hybridized critical coupling by Brillouin zone folding induced quasi-bound states in the continuum in bulk WS2 metasurfaces
- Spectroscopic evidence of competing diagonal spin interactions and spin disproportionation in the bilayer nickelate La 3 Ni 2 O 7
- Competing regimes of charge-carrier and impurity scattering limiting phonon heat conduction in heavily-doped silicon
BibTeX
@misc{vinther2026competing,
title = {{Competing pathways in polaritonic chemistry and general harmonic environments}},
author = {Jonas Vinther and Leonardo A. Cunha and Johannes Flick},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.04817},
eprint = {2610.04817},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.04817},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Competing pathways in polaritonic chemistry and general harmonic environments
AU - Jonas Vinther
AU - Leonardo A. Cunha
AU - Johannes Flick
PY - 2026
DA - 2026/10/03
PB - arXiv
DO - 10.48550/arxiv.2610.04817
UR - https://arxiv.org/abs/2610.04817
AB - Recent experiments suggest that strong light-matter coupling between molecules and cavity modes can significantly modify chemical reaction rates and yields. Despite multiple proposed mechanisms, a clear microscopic understanding of how vibrational strong coupling alters reaction kinetics remains incomplete. Here, we employ a general quantum-dynamical framework for analyzing competing reaction pathways in polaritonic chemistry by considering reaction coordinates with multiple relevant transition frequencies and general harmonic environments. We extend on a tensor-network formulation of the hierarchical equations of motion (HEOM) method to compute probability currents between vibrational states, leveraging a concise formulation for effective spectral densities and a controlled compression of Markovian bath modes into system-level jump operators. This allows us to decompose the resulting state-to-state probability currents, revealing how cavity-induced changes in individual transitions propagate through multistep reaction networks. We find that these local modifications can alter kinetic bottlenecks and selectively redistribute reaction flux between competing pathways, changing branching ratios under irreversible conditions without substantially affecting the equilibrium yield in the reversible regime. Finally, for coupled reaction-coordinate, spectator-mode, and cavity environments, we find structured, asymmetric rate profiles arising from interference between hybridized decay channels. Together, these results provide a mechanistic framework for understanding pathway-specific chemical reactivity under vibrational strong coupling.
ER -