Coupling Molecular Systems with Plasmonic Nanocavities: A Quantum Dynamics Approach

Jamshidi, Zahra; Kargar, Kimia; Mendive-Tapia, David; Vendrell, Oriol

doi:10.1021/acs.jpclett.3c02935

Cited by 3 publications

(2 citation statements)

References 76 publications

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“…The extension of similar approaches developed to study the photophysics of molecules and to investigate the optical properties of adsorbates with metal nanostructures has not been reported up to now. Actually, while we were completing this article, a paper appeared in the literature which used a similar model for simulating absorption spectra of a molecule in a nanocavity . Still, the application of this approach to EC-SERS documenting its ability to interpret experimental spectra is a novelty of the present contribution.…”

Section: Discussionmentioning

confidence: 99%

Linear Vibronic Coupling Approach for Surface-Enhanced Raman Scattering: Quantifying the Charge-Transfer Enhancement Mechanism

García-González,

Otero,

Ávila Ferrer

et al. 2024

J. Chem. Theory Comput.

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The outstanding amplification observed in surfaceenhanced Raman scattering (SERS) is due to several enhancement mechanisms, and standing out among them are the plasmonic (PL) and charge-transfer (CT) mechanisms. The theoretical estimation of the enhancement factors of the CT mechanism is challenging because the excited-state coupling between bright plasmons and dark CT states must be properly introduced into the model to obtain reliable intensities. In this work, we aim at simulating electrochemical SERS spectra, considering models of pyridine on silver clusters subjected to an external electric field E ⃗ that represents the effect of an electrode potential V el . The method adopts quantum dynamical propagations of nuclear wavepackets on the coupled PL and CT states described with linear vibronic coupling models parametrized for each E ⃗ through a fragment-based maximum-overlap diabatization. By presenting results at different values of E ⃗ , we show that indeed there is a relation between the population transferred to the CT states and the total scattered intensity. The tuning and detuning processes of the CT states with the bright PLs as a function of the electric field are in good agreement with those observed in experiments. Finally, our estimations for the CT enhancement factors predict values in the order of 10 5 to 10 6 , meaning that when the CT and PL states are both in resonance with the excitation wavelength, the CT and PL enhancements are comparable, and vibrational bands whose intensity is amplified by different mechanisms can be observed together, in agreement with what was measured by typical experiments on silver electrodes.

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Section: Discussionmentioning

confidence: 99%

Linear Vibronic Coupling Approach for Surface-Enhanced Raman Scattering: Quantifying the Charge-Transfer Enhancement Mechanism

García-González,

Otero,

Ávila Ferrer

et al. 2024

J. Chem. Theory Comput.

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“…An interesting avenue of research is the excited state dynamics and energy transfer processes between metal NPs and adsorbed molecules under various conditions. − In this context, the strong coupling regime is especially promising, since the initial eigenstates become thoroughly mixed, which leads to the formation of new energy states and potentially favorable electron transition possibilities . These changes of the electronic landscape yield modifications of reaction pathways, − allowing for modified chemistry, catalytic applications, or enhanced selectivity .…”

Section: Introductionmentioning

confidence: 99%

Origin of Macroscopic Observables of Strongly Coupled Metal Nanoparticle–Molecule Systems from Microscopic Electronic Properties

Bancerek,

Fojt,

Erhart

et al. 2024

J. Phys. Chem. C

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Strongly coupled light−matter systems are becoming a ubiquitous platform for investigating an increasing number of physical phenomena from modifying charge transport, altered emission, and relaxation pathways to selective or enhanced chemical reactivity. Such systems are investigated across a large length scale from few-nanometer-sized particles to macroscopic cavities encompassing many interacting moieties. Describing these numerous and varied physical systems is attempted in various ways from classical coupled harmonic oscillator models through quantum Hamiltonians to ab initio modeling. Here, by combining time-dependent density functional theory modeling and analysis with macroscopic models, we elucidate the origin of modifications of effective interaction parameters in terms of microscopic changes to the electronic density and Kohn−Sham transitions of the plasmonic particle and its coupled molecular counterpart. Specifically, we demonstrate how the emergence of mixed metal-molecular states and transitions modifies the effective resonances of the underlying plasmon and molecule in the regime of strong coupling and how these changes subsequently lead to the formation of mixed light−matter polaritons.

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Non-Hermitian molecular dynamics simulations of exciton–polaritons in lossy cavities

Sokolovskii,

Groenhof

2024

The Journal of Chemical Physics

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The observation that materials can change their properties when placed inside or near an optical resonator has sparked a fervid interest in understanding the effects of strong light–matter coupling on molecular dynamics, and several approaches have been proposed to extend the methods of computational chemistry into this regime. Whereas the majority of these approaches have focused on modeling a single molecule coupled to a single cavity mode, changes to chemistry have so far only been observed experimentally when very many molecules are coupled collectively to multiple modes with short lifetimes. While atomistic simulations of many molecules coupled to multiple cavity modes have been performed with semi-classical molecular dynamics, an explicit description of cavity losses has so far been restricted to simulations in which only a very few molecular degrees of freedom were considered. Here, we have implemented an effective non-Hermitian Hamiltonian to explicitly treat cavity losses in large-scale semi-classical molecular dynamics simulations of organic polaritons and used it to perform both mean-field and surface hopping simulations of polariton relaxation, propagation, and energy transfer.

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Coupling Molecular Systems with Plasmonic Nanocavities: A Quantum Dynamics Approach

Cited by 3 publications

References 76 publications

Linear Vibronic Coupling Approach for Surface-Enhanced Raman Scattering: Quantifying the Charge-Transfer Enhancement Mechanism

Linear Vibronic Coupling Approach for Surface-Enhanced Raman Scattering: Quantifying the Charge-Transfer Enhancement Mechanism

Origin of Macroscopic Observables of Strongly Coupled Metal Nanoparticle–Molecule Systems from Microscopic Electronic Properties

Non-Hermitian molecular dynamics simulations of exciton–polaritons in lossy cavities

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