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

---

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

---

Analytic model reveals local molecular polarizability changes induced by collective strong coupling in optical cavities

Physical Review Research, Год журнала: 2025, Номер 7(1)

Опубликована: Март 5, 2025

Despite recent numerical evidence, one of the fundamental theoretical mysteries polaritonic chemistry is how and if collective strong coupling can induce local changes electronic structure to modify chemical properties. Here we present nonperturbative analytic results for a model system consisting an ensemble N harmonic molecules under vibrational (VSC) that alters our understanding this question. By applying cavity Born-Oppenheimer partitioning on Pauli-Fierz Hamiltonian in dipole approximation, dressed many-molecule problem be solved nonperturbatively analytically dilute limit, i.e., self-consistent solution with mean-field Hartree-product wave function becomes exact. We discover molecular polarizabilities are modified even case vanishingly small single-molecule couplings. Consequently, polarization mechanism persists large-N limit. In contrast, perturbative calculation based uncoupled leads qualitatively erroneous scaling behavior vanishing effects large-N Nevertheless, exact (self-consistent) determined from simulations instead. Our observations demonstrate hitherto existing collective-scaling arguments insufficient they pave way refined single- (or few-)molecule strong-coupling systems coupling. Published by American Physical Society 2025

Язык: Английский

---

Understanding the cavity Born–Oppenheimer approximation

The Journal of Chemical Physics, Год журнала: 2024, Номер 160(18)

Опубликована: Май 8, 2024

Experiments have demonstrated that vibrational strong coupling between molecular vibrations and light modes can significantly change properties, such as ground-state reactivity. Theoretical studies toward the origin of this exciting observation roughly be divided into two categories, with based on Hamiltonians simply couple a molecule to cavity mode via its dipole moment one hand, other hand ab initio calculations self-consistently include effect electronic ground state within Born-Oppenheimer (CBO) approximation; these approaches are not equivalent. The CBO approach is more rigorous, but unfortunately it requires rewriting electronic-structure code, results may sometimes hard physically interpret. In work, we exploit relation demonstrate real (hydrogen fluoride) for realistic strengths, recover energies spectra high accuracy using only out-of-cavity quantities from standard calculations. doing so, discover what thephysical effects underlying are. Our methodology aid in incorporating possibly important features models, play pivotal role demystifying results, provide practical efficient alternative full

Язык: Английский

---

Collective Strong Coupling Modifies Aggregation and Solvation

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(5), С. 1428 - 1434

Опубликована: Янв. 30, 2024

Intermolecular (Coulombic) interactions are pivotal for aggregation, solvation, and crystallization. We demonstrate that the collective strong coupling of several molecules to a single optical mode results in notable changes molecular excitations around perturbed molecule, thus representing an impurity otherwise ordered system. A competition between short-range coulombic long-range photonic correlations inverts local transition density polaritonic state, suggesting polarizability solvation shell. Our provide alternative perspective on recent work chemistry pave way rigorous treatment cooperative effects

Язык: Английский

---

Cavity Quantum Electrodynamics Enables para- and ortho-Selective Electrophilic Bromination of Nitrobenzene

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(23), С. 16184 - 16193

Опубликована: Май 30, 2024

Coupling molecules to a quantized radiation field inside an optical cavity has shown great promise modify chemical reactivity. In this work, we show that the ground-state selectivity of electrophilic bromination nitrobenzene can be fundamentally changed by strongly coupling reaction cavity, generating ortho- or para-substituted products instead meta product. Importantly, these are not obtained from same outside cavity. A recently developed ab initio approach was used theoretically compute relative energies cationic Wheland intermediates, which indicate kinetically preferred site for all products. Performing analysis electron density intermediates and demonstrate how strong induces reorganization molecular charge distribution, in turn leads different sites directly dependent on conditions. Overall, results presented here understand induced changes reactivity mechanistic perspective as well connect frontier theoretical simulations state-of-the-art, but realistic, experimental

Язык: Английский

---

Realistic Ab Initio Predictions of Excimer Behavior under Collective Light-Matter Strong Coupling

Physical Review X, Год журнала: 2025, Номер 15(2)

Опубликована: Май 5, 2025

Experiments show that light-matter strong coupling affects chemical properties, though the underlying mechanism remains unclear. A major challenge is to perform reliable and affordable simulation of molecular behavior when many molecules are collectively coupled same optical mode. This paper presents an quantum electrodynamics cluster method for collective regime. The model describes electronic electron-photon correlation within a subsystem, while simplified description polaritonic excitations allows realistic microscopic coupling. developed framework provides computationally tractable route accurately simulate molecule in environment, which unfeasible several treated explicitly. We investigate properties argon dimer under In single-molecule regime (large coupling), potential energies substantially modified, weakening excimer bond. contrast, (small coupling, large number molecules), ground state energy surface first vibrational levels excited do not change significantly. However, produces abrupt transition landscape excimer, causing higher behave similarly vibrations state. expect formation be inhibited by conclude altered via distinct mechanisms regimes. also discuss fundamental aspects chemistry, such as resonance conditions sudden changes critical strength achieved. Published American Physical Society 2025

Язык: Английский

---

Phaseless Auxiliary-Field Quantum Monte Carlo Method for Cavity-QED Matter Systems

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Янв. 17, 2025

We present a generalization of the phaseless auxiliary-field quantum Monte Carlo (AFQMC) method to cavity quantum-electrodynamical (QED) matter systems. The can be formulated in both Coulomb and dipole gauge. verify its accuracy by benchmarking calculations on set small molecules against full configuration interaction state-of-the-art QED coupled cluster (QED–CCSD) calculations. Our results show that (i) gauge invariance achieved within correlation-consistent Gaussian basis sets, (ii) QED–CCSD enhanced significantly adding standard perturbative triples correction without light-matter coupling, (iii) there is straightforward way evaluate differential expression for photon occupation number works any high favorable computational scaling our AFQMC approach will enable broad range applications. Besides polaritonic chemistry, opens simulate extended

Язык: Английский

---

Stochastic resonance in vibrational polariton chemistry

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(6)

Опубликована: Фев. 10, 2025

In this work, we systematically investigate the impact of ambient noise intensity on rate modifications ground-state chemical reactions in an optical cavity under vibrational strong-coupling conditions. To achieve this, utilize a numerically exact open quantum system approach—the hierarchical equations motion twin space, combined with flexible tree tensor network state solver. Our findings reveal stochastic resonance phenomenon cavity-modified reactivities: optimal reaction enhancement occurs at intermediate level. other words, diminishes if noise, sensed by cavity–molecule through leakage, is either too weak or excessively strong. collective coupling regime, when weakly damped, strengthens as more molecules couple to cavity. contrast, strong damping, rates decline number grows.

Язык: Английский

---

Photon Many-Body Dispersion: Exchange-Correlation Functional for Strongly Coupled Light-Matter Systems

Physical Review Letters, Год журнала: 2025, Номер 134(7)

Опубликована: Фев. 21, 2025

We introduce an electron-photon exchange-correlation functional for quantum electrodynamical density-functional theory (QEDFT). The approach, photon MBD (pMBD), is inspired by the many-body dispersion (MBD) method weak intermolecular interactions, which generalized to include both electronic and photonic (electromagnetic) degrees of freedom on same footing. demonstrate that pMBD accurately captures effects arise in context strong light-matter such as anisotropic beyond single-photon effects, cavity-modulated van der Waals interactions. Moreover, we show computationally efficient allows simulations large complex systems coupled optical cavities.

Язык: Английский

---