The role of cavity losses on non-adiabatic couplings and dynamics in polaritonic chemistry

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

doi:10.26434/chemrxiv.12673259.v2

Cited by 2 publications

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

Section: Introductionmentioning

confidence: 99%

Nonadiabatic Dynamics in Multidimensional Complex Potential Energy Surfaces

Kossoski¹,

Barbatti

2020

Preprint

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<p>Despite the continuous development of theoretical methodologies for describing nonadiabatic dynamics of molecular systems, there is a lack of approaches for processes where the norm of the wave function is not conserved, i.e., when an imaginary potential accounts for some irreversible decaying mechanism. Current approaches rely on building potential energy surfaces of reduced dimensionality, which is not optimal for more involving and realistic multidimensional problems. Here, we present a novel methodology for describing the dynamics of complex-valued molecular Hamiltonians, which is a generalisation of the trajectory surface hopping method. As a first application, the complex surface fewest switches surface hopping (CS-FSSH) method was employed to survey the relaxation mechanisms of the shape resonant anions of iodoethene. We have provided the first detailed and dynamical picture of the π*/σ* mechanism of dissociative electron attachment in halogenated unsaturated compounds, which is believed to underlie electron-induced reactions of several molecules of interest. Electron capture into the π* orbital promotes C=C stretching and out-of-plane vibrations, followed by charge transfer from the double bond into the σ* orbital at the C-I bond, and, finally, release of the iodine ion, all within only 15 fs. On-the-fly dynamics simulations of a vast class of processes can be envisioned with the CS-FSSH methodology, including autoionisation from transient anions, core-ionised and superexcited states, Auger and interatomic Coulombic decay, and time-dependent luminescence.</p>

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Section: Introductionmentioning

confidence: 99%

Nonadiabatic Dynamics in Multidimensional Complex Potential Energy Surfaces

Kossoski¹,

Barbatti

2020

Preprint

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Photoprotecting Uracil by Coupling with Lossy Nanocavities

Felicetti

Fregoni

Schnappinger

et al. 2020

J. Phys. Chem. Lett.

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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.

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The role of cavity losses on non-adiabatic couplings and dynamics in polaritonic chemistry

Cited by 2 publications

References 0 publications

Nonadiabatic Dynamics in Multidimensional Complex Potential Energy Surfaces

Nonadiabatic Dynamics in Multidimensional Complex Potential Energy Surfaces

Photoprotecting Uracil by Coupling with Lossy Nanocavities

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