Molecular Chemistry in Cavity Strong Coupling

Chemical Reviews, Год журнала: 2023, Номер 123(13), С. 8099 - 8126

Опубликована: Июнь 30, 2023

The coherent exchange of energy between materials and optical fields leads to strong light-matter interactions so-called polaritonic states with intriguing properties, halfway light matter. Two decades ago, research on these interactions, using cavity (vacuum) fields, remained for the most part province physicist, a focus inorganic requiring cryogenic temperatures carefully fabricated, high-quality cavities their study. This review explores history recent acceleration interest in application molecular properties processes. enormous collective oscillator strength dense films organic molecules, aggregates, allows vacuum field coupling be achieved at room temperature, even rapidly highly lossy metallic cavities. has put associated phenomena fingertips laboratory chemists, scientists, biochemists as potentially new tool control chemistry. exciting that have emerged suggest are genuine relevance within material landscape.

Язык: Английский

---

Rovibrational Polaritons in Gas-Phase Methane

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(10), С. 5982 - 5987

Опубликована: Март 3, 2023

Polaritonic states arise when a bright optical transition of molecular ensemble is resonantly matched to an cavity mode frequency. Here, we lay the groundwork study behavior polaritons in clean, isolated systems by establishing new platform for vibrational strong coupling gas-phase molecules. We access regime intracavity cryogenic buffer gas cell optimized preparation simultaneously cold and dense ensembles report proof-of-principle demonstration methane. strongly cavity-couple individual rovibrational transitions probe range strengths detunings. reproduce our findings with classical transmission simulations presence absorbers. This infrastructure will provide testbed benchmark studies cavity-altered chemistry.

Язык: Английский

---

Unraveling a Cavity-Induced Molecular Polarization Mechanism from Collective Vibrational Strong Coupling

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(19), С. 5208 - 5214

Опубликована: Май 8, 2024

We demonstrate that collective vibrational strong coupling of molecules in thermal equilibrium can give rise to significant local electronic polarizations the thermodynamic limit. do so by first showing full nonrelativistic Pauli–Fierz problem an ensemble strongly coupled dilute-gas limit reduces cavity Born–Oppenheimer approximation a cavity–Hartree equation for structure. Consequently, each individual molecule experiences self-consistent dipoles all other molecules, which amount non-negligible values (large ensembles). Thus, alter localized "hotspots" within ensemble. Moreover, discovered cavity-induced polarization pattern possesses zero net polarization, resembles continuous form spin glass (or better glass). Our findings suggest thorough understanding polaritonic chemistry, requires treatment dressed structure, numerous, far overlooked, physical mechanisms.

Язык: Английский

---

Molecular Polaritons for Chemistry, Photonics and Quantum Technologies

Chemical Reviews, Год журнала: 2024, Номер 124(5), С. 2512 - 2552

Опубликована: Фев. 28, 2024

Molecular polaritons are quasiparticles resulting from the hybridization between molecular and photonic modes. These composite entities, bearing characteristics inherited both constituents, exhibit modified energy levels wave functions, thereby capturing attention of chemists in past decade. The potential to modify chemical reactions has spurred many investigations, alongside efforts enhance manipulate optical responses for quantum applications. This Review centers on experimental advances this burgeoning field. Commencing with an introduction fundamentals, including theoretical foundations various cavity architectures, we discuss outcomes polariton-modified reactions. Furthermore, navigate through ongoing debates uncertainties surrounding underpinning mechanism innovative method controlling chemistry. Emphasis is placed gaining a comprehensive understanding dynamics polaritons, particular, vibrational polaritons─a pivotal facet steering Additionally, unique capability coherent two-dimensional spectroscopy dissect polariton dark mode dynamics, offering insights into critical components within that alter We further expand utility applications as well precise manipulation polarizations, notably context chiral phenomena. discussion aspires ignite deeper curiosity engagement revealing physics properties, broad fascination harnessing environments control

Язык: Английский

---

Direct Observation of Polaritonic Chemistry by Nuclear Magnetic Resonance Spectroscopy

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 8, 2024

Abstract Polaritonic chemistry is emerging as a powerful approach to modifying the properties and reactivity of molecules materials. However, probing how electronics dynamics molecular systems change under strong coupling has been challenging due narrow range spectroscopic techniques that can be applied in situ. Here we develop microfluidic optical cavities for vibrational (VSC) are compatible with nuclear magnetic resonance (NMR) spectroscopy using standard liquid NMR tubes. VSC shown influence equilibrium between two conformations balance sensitive London dispersion forces, revealing an apparent constant VSC. In all compounds studied, does not induce detectable changes chemical shifts, J‐couplings, or spin‐lattice relaxation times. This unexpected finding indicates substantially affect electron density distributions, turn profound implications possible mechanisms at play polaritonic suggests emergence collective behavior critical.

Язык: Английский

---

Consequences of Vibrational Strong Coupling on Supramolecular Polymerization of Porphyrins

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(17), С. 12130 - 12137

Опубликована: Апрель 20, 2024

Supramolecular polymers display interesting optoelectronic properties and, thus, deploy multiple applications based on their molecular arrangement. However, controlling supramolecular interactions to achieve a desirable organization is not straightforward. Over the past decade, light-matter strong coupling has emerged as new tool for modifying chemical and material properties. This novel approach also been shown alter morphology of by vibrational bands solute solvent optical modes Fabry-Perot cavity (vibrational coupling, VSC). Here, we study effect VSC polymerization chiral zinc-porphyrins (

Язык: Английский

---

Diffusion quantum Monte Carlo approach to the polaritonic ground state

Physical review. A/Physical review, A, Год журнала: 2024, Номер 109(3)

Опубликована: Март 4, 2024

Making and using polaritonic states (i.e., hybrid electron-photon states) for chemical applications has recently become one of the most prominent active fields that connects communities chemistry quantum optics. Modeling such phenomena ab initio approaches calls new methodologies, leading to reinvention many commonly used electronic structure methods, as Hartree-Fock, density functional, coupled cluster theories. In this work, we explore formally exact diffusion Monte Carlo approach obtain numerical solutions ground state during dissociation ${\mathrm{H}}_{2}$ molecular system. We examine various electron-nuclear-photon properties throughout dissociation, changes minimum cavity Born-Oppenheimer surface, localization wave function, average mode occupation. Finally, directly compare our results obtained with state-of-the-art, yet approximate, approaches.

Язык: Английский

---

Unlocking Delocalization: How Much Coupling Strength can Overcome Energy Disorder in Molecular Polaritons?

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Polaritons lose delocalization in energetically disordered systems. A large Rabi splitting about 3–4 times of the inhomogeneous linewidths is required to restore delocalization. This study can guide future rational experiment designs.

Язык: Английский

---

Negligible rate enhancement from reported cooperative vibrational strong coupling catalysis

The Journal of Chemical Physics, Год журнала: 2021, Номер 155(24)

Опубликована: Дек. 13, 2021

We report the results of an attempt to reproduce a reported cavity catalysis ester hydrolysis para-nitrophenyl acetate due vibrational strong coupling. While we achieved same light-matter coupling strength and detuning, did not observe ten-fold increase in reaction rate constant. Furthermore, no obvious detuning dependence was observed. The inconsistency with literature suggests that is sensitive experimental details beyond onset This indicates other important factors are involved have been overlooked so far. find more investigation into limits, key factors, mechanisms reliably actualize modified reactions needed.

Язык: Английский

---

Resonant Cavity Modification of Ground-State Chemical Kinetics

The Journal of Physical Chemistry Letters, Год журнала: 2022, Номер 13(28), С. 6580 - 6586

Опубликована: Июль 14, 2022

Recent experiments have suggested that ground state chemical kinetics can be suppressed or enhanced by coupling the vibrational degrees of freedom a molecular system with radiation mode inside an optical cavity. Experiments show rate is strongly modified when photon frequency close to characteristic frequencies. The origin this remarkable effect remains unknown. In work, we develop analytical theory for cavity-modified based on Pollak-Grabert-H\"anggi theory. Unlike previous our covers complete range solvent friction values, from energy-diffusion limited spatial-diffusion regimes. We reaction either depending bath friction; weak as opposed case strong friction, where suppressed. Further, at which maximum modification achieved reactant well, and hence resonant occurs. limit {\it resonant} instead barrier frequency, obtained using Grote-Hynes Finally, observe changes (as function frequency) are much sharper more sizable in than limit, become increasingly sharp decreasing well frequency.

Язык: Английский

---