Toward a New Era of SERS and TERS at the Nanometer Scale: From Fundamentals to Innovative Applications

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(4), P. 1552 - 1634

Published: Feb. 6, 2023

Surface-enhanced Raman scattering (SERS) and tip-enhanced (TERS) have opened a variety of exciting research fields. However, although vast number applications been proposed since the two techniques were first reported, none has applied to real practical use. This calls for an update in recent fundamental application studies SERS TERS. Thus, goals scope this review are report new directions perspectives TERS, mainly from viewpoint combining their mechanism studies. Regarding progress discusses four main topics: (1) nanometer subnanometer plasmonic hotspots SERS; (2) Ångström resolved TERS; (3) chemical mechanisms, i.e., charge-transfer semiconductor-enhanced scattering; (4) creation strong bridge between applications.

Language: Английский

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Resonance Energy Transfer: From Fundamental Theory to Recent Applications

Frontiers in Physics, Journal Year: 2019, Volume and Issue: 7

Published: July 12, 2019

Resonance energy transfer (RET), the transport of electronic from one atom or molecule to another, has significant importance a number diverse areas science. Since pioneering experiments on RET by Cario and Franck in 1922, theoretical understanding process been continually refined. This review presents historical account post-Förster outlook RET, based quantum electrodynamics, up present-day viewpoint. It is through this framework that short-range, R–6 distance dependence Förster theory was unified with long range, radiative governed inverse-square law. Crucial knowledge electric dipole-electric dipole coupling tensor; we outline its mathematical derivation view explaining some key physical concepts RET. The higher order interactions involve magnetic dipoles quadrupoles are also discussed. To conclude, survey provided latest research, which includes between nanomaterials, enhancement due surface plasmons, possibilities outside usual ultraviolet visible range within cavity.

Language: Английский

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Tracking Polariton Relaxation with Multiscale Molecular Dynamics Simulations

The Journal of Physical Chemistry Letters, Journal Year: 2019, Volume and Issue: 10(18), P. 5476 - 5483

Published: Aug. 27, 2019

When photoactive molecules interact strongly with confined light modes in optical cavities, new hybrid light–matter states form. They are known as polaritons and correspond to coherent superpositions of excitations the cavity photon. The polariton energies thus potential energy surfaces changed respect bare molecules, such that formation is considered a promising paradigm for controlling photochemical reactions. To effectively manipulate photochemistry light, need remain polaritonic state long enough reaction on modified surface take place. understand what determines this lifetime, we have performed atomistic molecular dynamics simulations room-temperature ensembles rhodamine chromophores coupled single mode 15 fs lifetime. We investigated three popular experimental scenarios followed relaxation after optically pumping (i) lower polariton, (ii) upper or (iii) uncoupled states. results suggest lifetimes accessible limited by ultrafast photoemission due low lifetime reversible population transfer into "dark" manifold. Dark but much smaller contributions from photon, decreasing their emission rates hence increasing lifetimes. find between dark determined overlap absorption spectra. Importantly, excitation can also be transferred "upward" dark-state reservoir broad spectra chromophores, contrary common conception these processes "one-way" down polariton. Our chemistry relying taking place within manifold requires cavities sufficiently and, at same time, strong coupling strengths prevent back-transfer

Language: Английский

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Enhanced light–matter interaction in two-dimensional transition metal dichalcogenides

Reports on Progress in Physics, Journal Year: 2021, Volume and Issue: 85(4), P. 046401 - 046401

Published: Dec. 23, 2021

Two dimensional (2D) transition metal dichalcogenide (TMDC) materials, such as MoS2, WS2, MoSe2, and WSe2, have received extensive attention in the past decade due to their extraordinary physical properties. The unique properties make them become ideal materials for various electronic, photonic optoelectronic devices. However, performance is limited by relatively weak light-matter interactions atomically thin form factor. Resonant nanophotonic structures provide a viable way address this issue enhance 2D TMDCs. Here, we an overview of research area, showcasing relevant applications, including exotic light emission, absorption scattering features. We start overviewing concept excitons 1L-TMDC fundamental theory cavity-enhanced followed discussion on recent progress enhanced strong coupling valleytronics. nature enables broad range ways tune its electric optical Thus, continue reviewing advances TMDC-based tunable Next, survey over narrow bandwidths using 1L or few-layer TMDCs, applications photovoltaics photodetectors. also review efforts engineering scattering, e.g., inducing Fano resonances, wavefront TMDCs either integrating resonant structures, plasmonic/Mie metasurfaces, directly patterning monolayer/few layers then intriguing different types van der Waals heterostructures, Finally, draw our opinion potential opportunities challenges rapidly developing field research.

Language: Английский

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Theoretical Challenges in Polaritonic Chemistry

ACS Photonics, Journal Year: 2022, Volume and Issue: 9(4), P. 1096 - 1107

Published: Feb. 15, 2022

Polaritonic chemistry exploits strong light-matter coupling between molecules and confined electromagnetic field modes to enable new chemical reactivities. In systems displaying this functionality, the choice of cavity determines both confinement number that are involved in process. While wavelength-scale optical cavities interaction is ruled by collective effects, plasmonic subwavelength nanocavities allow even single reach coupling. Due these very distinct situations, a multiscale theoretical toolbox then required explore rich phenomenology polaritonic chemistry. Within framework, each component system (molecules modes) needs be treated sufficient detail obtain reliable results. Starting from general aspects light-molecule interactions typical experimental setups, we underline basic concepts should taken into account when operating area research. Building on considerations, provide map tools already available tackle applications molecular polaritons at different scales. Throughout discussion, draw attention successes challenges still ahead description

Language: Английский

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Reproducibility of cavity-enhanced chemical reaction rates in the vibrational strong coupling regime

The Journal of Chemical Physics, Journal Year: 2021, Volume and Issue: 154(19)

Published: May 18, 2021

One of the most exciting and debated aspects polariton chemistry is possibility that chemical reactions can be catalyzed by vibrational strong coupling (VSC) with confined optical modes in absence external illumination. Here, we report an attempt to reproduce enhanced rate cyanate ion hydrolysis reported Hiura et al. [chemRxiv:7234721 (2019)] when collective OH stretching vibrations water (which both solvent a reactant) are strongly coupled Fabry–Pérot cavity mode. Using piezo-tunable microcavity, vacuum Rabi splitting but fail observe any change reaction as thickness tuned out regime during given experiment. These findings suggest there subtleties involved successfully realizing VSC-catalyzed kinetics therefore motivate broader effort within community validate claims dark.

Language: Английский

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Intermolecular interactions in optical cavities: An ab initio QED study

The Journal of Chemical Physics, Journal Year: 2021, Volume and Issue: 154(9)

Published: March 2, 2021

Intermolecular bonds are weak compared to covalent bonds, but they strong enough influence the properties of large molecular systems. In this work, we investigate how light-matter coupling inside an optical cavity can modify these intermolecular forces. We perform a detailed comparison between currently available ab initio electron-photon methodologies. The electromagnetic field modulate ground state weakly bound complexes. Controlling polarization, interactions be stabilized or destabilized, and electron densities, dipole moments, polarizabilities altered. demonstrate that correlation is fundamental describe in coupling. This work proposes cavities as novel tool manipulate control properties, solvent effects, for molecules materials.

Language: Английский

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Optical Metasurfaces for Energy Conversion

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(19), P. 15082 - 15176

Published: June 21, 2022

Nanostructured surfaces with designed optical functionalities, such as metasurfaces, allow efficient harvesting of light at the nanoscale, enhancing light–matter interactions for a wide variety material combinations. Exploiting light-driven matter excitations in these artificial materials opens up new dimension conversion and management energy nanoscale. In this review, we outline impact, opportunities, applications, challenges metasurfaces converting incoming photons into frequency-shifted photons, phonons, energetic charge carriers. A myriad opportunities await utilization converted energy. Here cover most pertinent aspects from fundamental nanoscopic viewpoint all way to applications.

Language: Английский

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Catalysis by Dark States in Vibropolaritonic Chemistry

Physical Review Letters, Journal Year: 2022, Volume and Issue: 128(9)

Published: Feb. 28, 2022

Collective strong coupling between a disordered ensemble of N localized molecular vibrations and resonant optical cavity mode gives rise to two polariton N-1≫2 dark modes. Thus, experimental changes in thermally activated reaction kinetics due formation appear entropically unlikely remain puzzle. Here we show that the overlooked modes, while parked at same energy as bare vibrations, are robustly delocalized across ∼2-3 molecules, yielding enhanced channels vibrational cooling, concomitantly catalyzing chemical reaction. As an illustration, theoretically ≈50% increase electron transfer rate product stabilization. The reported effects can arise when homogeneous linewidths modes smaller than their spacings.

Language: Английский

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Vibration-Cavity Polariton Chemistry and Dynamics

Annual Review of Physical Chemistry, Journal Year: 2022, Volume and Issue: 73(1), P. 429 - 451

Published: Jan. 26, 2022

Molecular polaritons result from light-matter coupling between optical resonances and molecular electronic or vibrational transitions. When the is strong enough, new hybridized states with mixed photon-material character are observed spectroscopically, shifted above below uncoupled frequency. These modes have unique properties can be exploited to promote inhibit physical chemical processes. One remarkable that cavities alter reaction rates product branching ratios no excitation whatsoever. In this work we review ability of vibration-cavity modify processes including reactivity, as well steady-state transient spectroscopy. We discuss larger context these works highlight their most important contributions implications. Our goal provide insight for systematically manipulating in photonic applications.

Language: Английский

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