Simulating anharmonic vibrational polaritons beyond the long wavelength approximation

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(1)

Published: Jan. 2, 2025

In this work, we investigate anharmonic vibrational polaritons formed due to strong light–matter interactions in an optical cavity between radiation modes and vibrations beyond the long-wavelength limit. We introduce a conceptually simple description of interactions, where spatially localized couple vibrations. Within theoretical framework, employ self-consistent phonon theory dynamical mean-field efficiently simulate momentum-resolved vibrational-polariton spectra, including effects anharmonicity. Numerical simulations model systems demonstrate accuracy applicability our approach.

Language: Английский

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Light–matter interaction Hamiltonians in cavity quantum electrodynamics

Chemical Physics Reviews, Journal Year: 2025, Volume and Issue: 6(1)

Published: Feb. 12, 2025

When matter is strongly coupled to an optical cavity, new hybrid light–matter states are formed, the so-called polariton states. These polaritons can qualitatively change physical properties of cavity by completely altering its energy eigenspectrum. Fueled experimental innovations in recent years, much progress has been made simulating intrinsic quantum behavior these At heart each simulation choice Hamiltonian represent total system. Even at this fundamental level, there significant developing gauges and representations for Hamiltonian, whether exact or under approximations. As such, review aims discuss several different forms Hamiltonians researcher trying enter field clearly concisely deriving representation from Minimal Coupling Hamiltonian. In addition, provides commentary on optimal usage extent approximations individual assist reader choosing appropriate their work.

Language: Английский

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Do Molecular Geometries Change Under Vibrational Strong Coupling?

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(30), P. 7700 - 7707

Published: July 23, 2024

As pioneering experiments have shown, strong coupling between molecular vibrations and light modes in an optical cavity can significantly alter properties even affect chemical reactivity. However, the current theoretical description is limited far from complete. To explore origin of this exciting observation, we investigate how structure changes under light-matter using ab initio method based on Born-Oppenheimer Hartree-Fock ansatz. By optimizing H2O H2O2 resonantly coupled to modes, study importance reorientation geometric relaxation. In addition, show that inclusion one or two change observed results. On basis our findings, derive a simple concept estimate effect interaction geometry polarizability dipole moments.

Language: Английский

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Polariton-induced Purcell effects via a reduced semiclassical electrodynamics approach

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

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Comparing parameterized and self-consistent approaches to ab initio cavity quantum electrodynamics for electronic strong coupling

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(17)

Published: Nov. 1, 2024

Molecules under strong or ultra-strong light–matter coupling present an intriguing route to modify chemical structure, properties, and reactivity. A rigorous theoretical treatment of such systems requires handling matter photon degrees freedom on equal quantum mechanical footing. In the regime molecular electronic one a few molecules, it is desirable treat using tools ab initio chemistry, yielding approach referred as cavity electrodynamics (ai-QED), where are treated at level QED. We analyze two complementary approaches ai-QED: (1) parameterized ai-QED, two-step computed existing structure theories, enabling construction ai-QED Hamiltonians in basis many-electron eigenstates, (2) self-consistent one-step methods generalized include between freedom. Although these equivalent their exact limits, we identify disparity projection two-body dipole self-energy operator that appears its counterpart approach. provide argument this resolves only limit complete orbital for projection. numerical results highlighting resolution particularly simple system helium hydride cation, possible limits simultaneously. same system, examine compare practical issue computational cost required converge each toward bases limit. Finally, assess aspect photonic convergence polar charged species, finding comparable behavior approaches.

Language: Английский

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Perturbative analysis of the coherent state transformation in ab initio cavity quantum electrodynamics

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

Published: Nov. 18, 2024

Experimental demonstrations of modified chemical structure and reactivity under strong light-matter coupling have spurred theoretical computational efforts to uncover underlying mechanisms. Ab initio cavity quantum electrodynamics (QED) combines chemistry with QED investigate these phenomena in detail. Unitary transformations ab Hamiltonians been used make them more computationally tractable. We analyze one such transformation, the coherent state using perturbation theory. Applying theory up third order for ground energies potential energy surfaces several molecular systems electronic coupling, we show that transformation yields better agreement exact energies. examine specific case ninth find performs fifth but converges slowly at higher orders. In addition, apply second mode states bilinear elucidating how accelerates convergence photonic subspace toward complete basis limit renders ion origin invariant. These findings contribute valuable insights into advantages context methods.

Language: Английский

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Comparing parameterized and self-consistent approaches to ab inito CQED for electronic strong coupling

Published: June 6, 2024

Molecules under strong or ultra-strong light-matter coupling present an intriguing route to modify chemical structure, properties, and reactivity. A rigorous theoretical treatment of such systems requires handling matter photon degrees freedom on equal quantum mechanical footing. In the regime molecular electronic one a few molecules, it is desirable treat using tools ab initio chemistry, yielding approach referred as cavity electrodynamics (ai-QED), where are treated at level electrodynamics. this letter, we analyze two complementary approaches ai-QED: (1) parameterized CQED (pQED), two-step computed existing structure theories, enabling construction ai-QED Hamiltonians in basis many-electron eigenstates, (2) self-consistent (scQED), one-step methods generalized include between freedom. Although these equivalent their exact limits, identify disparity projection two-body dipole self-energy operator that appears pQED its counterpart scQED approach. We provide argument resolves only limit complete orbital for projection. numerical results highlighting resolution simple systems, possible limits simultaneously. Additionally, examine compare practical issue computational cost required converge each towards bases.

Language: Английский

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Comparing parameterized and self-consistent approaches to ab initio cavity quantum electrodynamics for electronic strong coupling

Published: July 25, 2024

Molecules under strong or ultra-strong light-matter coupling present an intriguing route to modify chemical structure, properties, and reactivity. A rigorous theoretical treatment of such systems requires handling matter photon degrees freedom on equal quantum mechanical footing. In the regime molecular electronic one a few molecules, it is desirable treat using tools ab initio chemistry, yielding approach referred as cavity electrodynamics (ai-QED), where are treated at level electrodynamics. We analyze two complementary approaches ai-QED: (1) parameterized ai-QED, two-step computed existing structure theories, enabling construction ai-QED Hamiltonians in basis many-electron eigenstates, (2) self-consistent one-step methods generalized include between freedom. Although these equivalent their exact limits, we identify disparity projection two-body dipole self-energy operator that appears its counterpart approach. provide argument this resolves only limit complete orbital for projection. numerical results highlighting resolution particularly simple system helium hydride cation, possible limits simultaneously. same system, examine compare practical issue computational cost required converge each towards bases limit. Finally, assess aspect photonic convergence polar charged species, finding comparable behavior approaches.

Language: Английский

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Perturbative analysis of the coherent state transformation in ab initio cavity quantum electrodynamics

Published: Aug. 16, 2024

Experimental demonstrations of modified chemical structure and reactivity under strong light-matter coupling have spurred theoretical computational efforts to uncover underlying mechanisms. Ab initio cavity quantum electrodynamics (QED) combines chemistry with QED investigate these phenomena in detail. Unitary transformations ab Hamiltonians been used make them more computationally tractable. We analyze one such transformation, the coherent state using perturbation theory. Applying theory up third order for ground energies potential energy surfaces electronic coupling, we show that transformation yields better agreement exact energies. Additionally, apply second mode states bilinear elucidating how accelerates convergence photonic subspace towards complete basis limit renders molecular ion origin invariant. These findings contribute valuable insights into advantages context methods.

Language: Английский

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Unraveling abnormal collective effects via the non-monotonic number dependence of electron transfer in confined electromagnetic fields

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(10)

Published: Sept. 9, 2024

Strong light–matter coupling within an optical cavity leverages the collective interactions of molecules and confined electromagnetic fields, giving rise to possibilities modifying chemical reactivity molecular properties. While responses, such as enhanced Rabi splitting, are often observed, overall effect on systems remains ambiguous for a large number molecules. In this paper, we investigate non-adiabatic electron transfer process in donor–acceptor pairs influenced by excitation local dynamics. Using timescale difference between reorganization thermal fluctuations, derive analytical formulas rate constant polariton relaxation rate. These apply any (N) account induced photon coupling. Our findings reveal non-monotonic dependence N, which can be understood interplay relaxation. As result, cavity-induced quantum yield increases linearly with N small (as predicted simple Dicke model) but shows turnover suppression N. We also interrelate bath frequency molecules, suggesting optimal maximizing enhancement. The analysis provides insight understanding light transfer, helping predict condition effective cavity-controlled reactivity.

Language: Английский

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