Multiple interacting photonic modes in strongly coupled organic microcavities DOI Creative Commons
Felipe Herrera, William L. Barnes

Philosophical Transactions of the Royal Society A Mathematical Physical and Engineering Sciences, Journal Year: 2024, Volume and Issue: 382(2287)

Published: Dec. 24, 2024

Room-temperature cavity quantum electrodynamics with molecular materials in optical cavities offers exciting prospects for controlling electronic, nuclear and photonic degrees of freedom applications physics, chemistry science. However, achieving strong coupling ensembles typically requires high densities substantial electromagnetic-field confinement. These conditions usually involve a significant degree disorder highly structured density states. It remains unclear to what extent these additional complexities modify the usual physical picture developed atoms inorganic semiconductors. Using microscopic description realistic multimode resonators, we show that emergence vacuum Rabi splitting linear spectroscopy is necessary but not sufficient metric coherent admixing between light matter. In low-finesse multi-mode situations, find dipoles can be partially hybridized dissipation channels associated off-resonant modes. vacuum-induced dissipative processes ultimately limit light-matter coherence system sustain. This article part theme issue ‘The theory light’.

Language: Английский

Polariton-induced Purcell effects via a reduced semiclassical electrodynamics approach DOI

Andres Vargas,

Tao E. Li

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(12)

Published: March 24, 2025

Recent experiments have demonstrated that polariton formation provides a novel strategy for modifying local molecular processes when large ensemble of molecules is confined within an optical cavity. Herein, numerical based on coupled Maxwell–Schrödinger equations examined simulating in realistic cavity structure under collective strong coupling. In this approach, only few molecules, referred to as quantum impurities, are treated mechanically, while the remaining macroscopic layer and modeled using dielectric functions. When single electronic two-level system embedded Lorentz medium two-dimensional Bragg resonator, our simulations reveal polariton-induced Purcell effect: radiative decay rate impurity significantly enhanced by frequency matches frequency, can sometimes be greatly suppressed near resonance with bulk forming addition, approach demonstrates absorption light exhibits Rabi-splitting-dependent suppression due inclusion structure. Our also identify fundamental limitation approach—an inaccurate description dephasing rates into dark modes. This arises because dark-mode degrees freedom not explicitly included most simple As effect alters differently from weak coupling, may facilitate understanding origin polariton-modified photochemistry

Language: Английский

Citations

0
Measuring Kinetics under Vibrational Strong Coupling: Testing for a Change in the Nucleophilicity of Water and Alcohols DOI Creative Commons
Cyprien Muller, Robert J. Mayer, Maciej Piejko

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(49)

Published: Aug. 21, 2024

Abstract Vibrational Strong Coupling (VSC) has been reported to change the rate of organic reactions. However, a lack convenient and reliable methods measure reaction kinetics under VSC makes it challenging obtain mechanistic insight into its influence, hindering progress in field. Here, we use recently developed fixed‐width optical cavities large kinetic datasets with small errors (±1–5 %) an operationally simple manner using UV/Vis spectroscopy. The setup is used test whether changes fundamental property polar reactions, nucleophilicity, for water alcohols, species commonly VSC‐modified chemistry. We determined constants nucleophilic capture library benzhydrilium ions as reference electrophiles without strong coupling nucleophile's key vibrations. For all investigated combinations nucleophiles, only minor observed reactions were independently coupled bands. These results indicate that does not substantially alter nucleophilicity suggesting are modified through other, presently unknown mechanisms. Fixed‐width allow reproducible kinetics, facilitating studies

Language: Английский

Citations

2
Impact of Cavity Length Non-uniformity on Reaction Rate Extraction in Strong Coupling Experiments DOI
Michael A. Michon, Blake S. Simpkins

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(44), P. 30596 - 30606

Published: Oct. 28, 2024

Reports of altered chemical phenomena under vibrational strong coupling, including reaction rates, product distributions, intermolecular forces, and cavity-mediated energy transfer, have been met with a great deal skepticism due to several irreproducible results the lack an accepted theoretical framework. In this work, we add some insight by identifying UV-vis measurement artifact that distorts observed absorption peak positions, amplitudes, consequently, rates extracted in optical microcavities. We predict characterize behavior using Transfer Matrix (TM) method confirm its presence experimentally. then present correction technique whereby effective molar coefficient is assigned absorbing species within cavity. These revelations important implications for many existing examples cavity-modified chemistry establishing best practices carrying out robust future investigations.

Language: Английский

Citations

2
Measuring Kinetics under Vibrational Strong Coupling: Testing for a Change in the Nucleophilicity of Water and Alcohols DOI Creative Commons
Cyprien Muller, Robert J. Mayer, Maciej Piejko

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(49)

Published: Aug. 21, 2024

Abstract Vibrational Strong Coupling (VSC) has been reported to change the rate of organic reactions. However, a lack convenient and reliable methods measure reaction kinetics under VSC makes it challenging obtain mechanistic insight into its influence, hindering progress in field. Here, we use recently developed fixed‐width optical cavities large kinetic datasets with small errors (±1–5 %) an operationally simple manner using UV/Vis spectroscopy. The setup is used test whether changes fundamental property polar reactions, nucleophilicity, for water alcohols, species commonly VSC‐modified chemistry. We determined constants nucleophilic capture library benzhydrilium ions as reference electrophiles without strong coupling nucleophile's key vibrations. For all investigated combinations nucleophiles, only minor observed reactions were independently coupled bands. These results indicate that does not substantially alter nucleophilicity suggesting are modified through other, presently unknown mechanisms. Fixed‐width allow reproducible kinetics, facilitating studies

Language: Английский

Citations

2
Erratum: “Strong coupling-induced frequency shifts of highly detuned photonic modes in multimode cavities” [J. Chem. Phys. 160, 204303 (2024)] DOI
Philip A. Thomas, William L. Barnes

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(3)

Published: July 15, 2024

Language: Английский

Citations

1
Controlling and Probing Molecular Polaritons DOI Creative Commons
Blake S. Simpkins, Michael A. Michon

Published: Aug. 5, 2024

The goal of this chapter is to accelerate the ability research groups contribute quickly, accurately, and substantively, field cavity-modified materials behaviors. opportunity tune fundamental chemical physical properties with an engineered optical environment has inspired images designer cavity-catalysis, enhanced energy technologies, directed bio-assembly. Although numerous demonstrations chemistry have been made, hesitancy remains due a lack mechanistic understanding, experimentally precarious results, general enigmatic character phenomenon. In fact, corroborating results met doubt by even close colleagues. However, just as error bars are slowly shaved away, measurement measurement, eventually reveal sought-after truth, so too must we continue evaluate cavity-induced effects, troubleshooting improving experimental techniques, refining analytical tools, listening addressing legitimate criticism.

Language: Английский

Citations

1
Cavity induced modulation of intramolecular vibrational energy flow pathways DOI
Subhadip Mondal, Srihari Keshavamurthy

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(19)

Published: Nov. 15, 2024

Recent experiments in polariton chemistry indicate that reaction rates can be significantly enhanced or suppressed inside an optical cavity. One possible explanation for the rate modulation involves cavity mode altering intramolecular vibrational energy redistribution (IVR) pathways by coupling to specific molecular vibrations strong (VSC) regime. However, mechanism such a cavity-mediated of IVR is yet understood. In recent study, Ahn et al. [Science 380, 1165 (2023)] observed alcoholysis phenyl isocyanate (PHI) considerably when tuned resonant with (NCO) stretching PHI. Here, we analyze quantum and classical dynamics model effective Hamiltonian PHI involving high-frequency NCO-stretch two key low-frequency ring modes. We compute various indicators extent cavity–molecule system show tuning frequency NCO-stretching strongly perturbs cavity-free pathways. Subsequent anharmonic resonances lead efficient scrambling initial overtone state over number space. also hybrid light–matter states undergo localization–delocalization transition VSC

Language: Английский

Citations

1
Vibrational strong coupling of organic molecules embedded within graphene plasmon nanocavities facilitated by perfect absorbers DOI

Zhiyong Wu,

Baiquan Liu, Shaolin Liao

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(23)

Published: Dec. 16, 2024

The strong coupling between infrared photonic resonances and vibrational transitions of organic molecules is called (VSC), which presents attractive prospects for modifying molecular chemical characteristics behaviors. Currently, VSC studies suffer from limited bandwidth or enormous mode volumes. In addition, in certain instances, the absorption spectrum weaker, thus impeding effective monitoring effect. Here, we theoretically study effect by embedding 5-nm-thick into a graphene plasmon nanocavity (GPNC). Pronounced anti-crossing with Rabi splitting exceeding 80 cm-1 are disclosed spectra coupled system, benefiting ultra-small volume provided GPNC. Further assembling GPNC perfect absorber configuration can significantly enhance spectral peaks effect, maximizing reachability phenomenon. Furthermore, tunability enables changes electrically adjusting graphene's Fermi level structure fixed geometric parameters. establish an analytical framework alignment computational simulations to elucidate triggering criteria mode, thereby giving clear picture understanding physical processes that form mode. Given supports modes across extensive range extending terahertz, suggested suitable investigating diverse materials.

Language: Английский

Citations

0
Multiple interacting photonic modes in strongly coupled organic microcavities DOI Creative Commons
Felipe Herrera, William L. Barnes

Philosophical Transactions of the Royal Society A Mathematical Physical and Engineering Sciences, Journal Year: 2024, Volume and Issue: 382(2287)

Published: Dec. 24, 2024

Room-temperature cavity quantum electrodynamics with molecular materials in optical cavities offers exciting prospects for controlling electronic, nuclear and photonic degrees of freedom applications physics, chemistry science. However, achieving strong coupling ensembles typically requires high densities substantial electromagnetic-field confinement. These conditions usually involve a significant degree disorder highly structured density states. It remains unclear to what extent these additional complexities modify the usual physical picture developed atoms inorganic semiconductors. Using microscopic description realistic multimode resonators, we show that emergence vacuum Rabi splitting linear spectroscopy is necessary but not sufficient metric coherent admixing between light matter. In low-finesse multi-mode situations, find dipoles can be partially hybridized dissipation channels associated off-resonant modes. vacuum-induced dissipative processes ultimately limit light-matter coherence system sustain. This article part theme issue ‘The theory light’.

Language: Английский

Citations

0