The Role of Cavity Losses in Polaritonic Chemistry

Antoniou, Panayiota; Suchanek, Figen; Varner, James F.; Foley, Jonathan J.

doi:10.26434/chemrxiv.12673259.v1

Cited by 4 publications

(4 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In a more general perspective, we demonstrate that better cavities do not necessarily correspond to improved photochemistry. Similar non-Hermitian schemes to investigate cavity losses in polaritonic chemistry have been independently developed by Foley and collaborators for the azobenzene molecule and by Ulusoya and Vendrell for NaI and pyrazine molecules.…”

mentioning

confidence: 99%

Photoprotecting Uracil by Coupling with Lossy Nanocavities

Felicetti

Fregoni

Schnappinger

et al. 2020

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

We analyze how the photorelaxation dynamics of a molecule can be controlled by modifying its electromagnetic environment using a nanocavity mode. In particular, we consider the photorelaxation of the RNA nucleobase uracil, which is the natural mechanism to prevent photodamage. In our theoretical work, we identify the operative conditions in which strong coupling with the cavity mode can open an efficient photoprotective channel, resulting in a relaxation dynamics twice as fast as the natural one. We rely on a state-of-the-art chemically detailed molecular model and a non-Hermitian Hamiltonian propagation approach to perform full-quantum simulations of the system dissipative dynamics. By focusing on the photon decay, our analysis unveils the active role played by cavity-induced dissipative processes in modifying chemical reaction rates, in the context of molecular polaritonics. Remarkably, we find that the photorelaxation efficiency is maximized when an optimal trade-off between light–matter coupling strength and photon decay rate is satisfied. This result is in contrast with the common intuition that increasing the quality factor of nanocavities and plasmonic devices improves their performance. Finally, we use a detailed model of a metal nanoparticle to show that the speedup of the uracil relaxation could be observed via coupling with a nanosphere pseudomode, without requiring the implementation of complex nanophotonic structures.

show abstract

mentioning

confidence: 99%

Photoprotecting Uracil by Coupling with Lossy Nanocavities

Felicetti

Fregoni

Schnappinger

et al. 2020

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

show abstract

“…Spontaneous emission manifests in finite excited cavity mode lifetimes (Finite lifetimes of molecular rovibrational states are neglected in what follows). These are considered here by a phenomenological approach recently employed in electronic strong coupling studies [40][41][42]. There, the cavity mode Hamiltonian, ĤC , is replaced by a non-Hermitian operator…”

Section: Cavity Loss Effectsmentioning

confidence: 99%

Cavity-induced Non-Adiabatic Dynamics and Spectroscopy of Molecular Rovibrational Polaritons studied by Multi-Mode Quantum Models

Fischer,

Saalfrank

2022

Preprint

View full text Add to dashboard Cite

We study theoretically the quantum dynamics and spectroscopy of rovibrational polaritons formed in a single rovibrating diatomic molecule, which interacts with two degenerate, orthogonally polarized modes of an optical Fabry-Pérot cavity. We employ an effective rovibrational Pauli-Fierz Hamiltonian in length gauge representation and identify three-state vibro-polaritonic conical intersections (VPCIs) between singly-excited vibro-polaritonic states in a two-dimensional angular coordinate branching space. The lower and upper vibrational polaritons are of mixed light-matter hybrid character, whereas the intermediate state is purely photonic in nature. The VPCIs provide effective population transfer channels between singly-excited vibrational polaritons, which manifest in rich interference patterns in rotational densities. Spectroscopically, three bright singly-excited states are identified, when an external infrared laser field couples to both a molecular and a cavity mode. The non-trivial VPCI topology manifests as pronounced multi-peak progression in the spectral region of the upper vibrational polariton, which is traced back to the emergence of rovibropolaritonic light-matter hybrid states. Experimentally ubiquitous spontaneous emission from cavity modes induces a dissipative reduction of intensity and peak broadening, which mainly influences the purely photonic intermediate state peak as well as the rovibro-polaritonic progression.

show abstract

“…Then, we demonstrate its potential by surveying the dynamics of a resonant state in an actual molecular system. We mention an independent development 18 where the FSSH approach was applied to complexvalued PESs. There, the authors have employed a onedimensional model to describe cavity losses in the polaritonic dynamics of azobenzene.…”

Section: Introductionmentioning

confidence: 99%