Blackbody Radiation and Thermal Effects on Chemical Reactions and Phase Transitions in Cavities

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

An important question in polariton chemistry is whether reacting molecules are thermal equilibrium with their surroundings. If not, can experimental changes observed reaction rates of a cavity (even without optical pumping) be attributed to higher/lower temperature inside the cavity? In this work, we address by computing differences between and air outside. We found difference negligible for most reactions. On other hand, phase transitions cavities, as material actively maintained heating/cooling source experiments, show that cavities modify transition temperatures when mirrors windows ideal (nonabsorbing); however, modification vanishes real used. This conclusion relies on having low contact resistance molecules. Finally, find substantial blackbody spectral energy density free space infrared which reveal resonance effects could potentially play role explaining chemical reactivity dark.

Language: Английский

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Quantum Floquet engineering with an exactly solvable tight-binding chain in a cavity

Communications Physics, Journal Year: 2022, Volume and Issue: 5(1)

Published: May 19, 2022

Abstract Recent experimental advances enable the manipulation of quantum matter by exploiting nature light. However, paradigmatic exactly solvable models, such as Dicke, Rabi or Jaynes-Cummings models for quantum-optical systems, are scarce in corresponding solid-state, materials context. Focusing on long-wavelength limit light, here, we provide an model given a tight-binding chain coupled to single cavity mode via quantized version Peierls substitution. We show that perturbative expansions light-matter coupling have be taken with care and can easily lead false superradiant phase. Furthermore, analytical expression groundstate thermodynamic limit, which photons squeezed coupling. In addition, derive expressions electronic single-particle spectral function optical conductivity. unveil Floquet engineering signatures these dynamical response functions, analogs localization replica side bands, complementing classical results. Strikingly, Drude weight conductivity electrons is partially suppressed presence through induced electron-electron interaction.

Language: Английский

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Disorder enhanced vibrational entanglement and dynamics in polaritonic chemistry

Communications Physics, Journal Year: 2022, Volume and Issue: 5(1)

Published: May 17, 2022

Abstract Collectively coupling molecular ensembles to a cavity has been demonstrated modify chemical reactions akin catalysis. Theoretically understanding this experimental finding remains an important challenge. In particular the role of quantum effects in such setups is open question fundamental and practical interest. Theoretical descriptions often neglect entanglement between nuclear electro-photonic degrees freedom, e.g., by computing Ehrenfest dynamics. Here we discover that disorder can strongly enhance build-up on short timescales after incoherent photo-excitation. We find have direct consequences for coordinate analyze phenomenon disordered Holstein-Tavis-Cummings model, minimal toy model includes all freedom. Using numerical technique based matrix product states simulate exact dynamics more than 100 molecules. Our results highlight importance beyond Born-Oppenheimer theories polaritonic chemistry.

Language: Английский

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Polaritonic Chemistry from First Principles via Embedding Radiation Reaction

The Journal of Physical Chemistry Letters, Journal Year: 2022, Volume and Issue: 13(30), P. 6905 - 6911

Published: July 22, 2022

The coherent interaction of a large collection molecules with common photonic mode results in strong light-matter coupling, feature that proved highly beneficial for chemistry and termed the research topics polaritonic QED chemistry. Considering complex microscopic chemical reactions combination macroscopic number renders existing ab initio approaches inapplicable. In this work, I introduce simple approach to capture collective nature while retaining full representation single molecules. By embedding majority molecular ensemble into dyadic Green tensor, we obtain computationally cheap intuitive description dynamic molecule - an seems ideal introduced radiation-reaction potential is thoroughly discussed, including prospects, applications limitations. A first application demonstrates linear response are part larger ensembles Then, by virtue proton-tunneling model, illustrate influence coupling on features nontrivial dependence emitters. Bridging classical electrodynamics, quantum optical descriptions realistic molecules, work can serve as guiding light future developments investigations quickly growing fields material design.

Language: Английский

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Wavefunction embedding for molecular polaritons

The Journal of Chemical Physics, Journal Year: 2022, Volume and Issue: 157(9)

Published: July 5, 2022

Polaritonic chemistry relies on the strong light-matter interaction phenomena for altering chemical reaction rates inside optical cavities. To explain and understand these processes, development of reliable theoretical models is essential. While computationally efficient quantum electrodynamics self-consistent field (QED-SCF) methods, such as density functional theory, need accurate functionals, coupled cluster (QED-CC) methods provide a systematic increase in accuracy but at much greater cost. overcome this computational bottleneck, herein we introduce develop QED-CC-in-QED-SCF projection-based embedding method that inherits all favorable properties from two worlds: efficiency accuracy. The performance assessed by studying some prototypical relevant reactions, methyl transfer reaction, proton protonation complex environment. results obtained with new are excellent agreement more expensive QED-CC results. analysis performed reactions indicates electron-photon correlation effects local nature only small region should be treated level capturing important due to cavity. This work sets stage future developments polaritonic will serve guideline other models.

Language: Английский

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