Changing Vibration Coupling Strengths of Liquid Acetonitrile with an Angle-Tuned Etalon

Erwin, Justin D.; Wang, Ying; Bradley, Rebecca C.; Coe, James V.

doi:10.1021/acs.jpcb.1c01758

Cited by 6 publications

(22 citation statements)

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“…This effectively correlates the vibrations along the chain protecting the Si-C bond. In a similar spirit, Erwin et al 45 demonstrated that strong coupling can alter the anharmonic coupling between vibrational excitations while Sun and Vendrell 46 recovered the effect of cavity-mediated energy-redistribution for the cis-trans isomerization of HONO. The dominant effect of vibrational strong coupling on a ground-state chemical reaction would be therefore that it provides means to alter the redistribution of energy from a specific bond into other degrees of freedom.…”

Section: Resultsmentioning

confidence: 90%

Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity

et al. 2022

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Strong light–matter interaction in cavity environments is emerging as a promising approach to control chemical reactions in a non-intrusive and efficient manner. The underlying mechanism that distinguishes between steering, accelerating, or decelerating a chemical reaction has, however, remained unclear, hampering progress in this frontier area of research. We leverage quantum-electrodynamical density-functional theory to unveil the microscopic mechanism behind the experimentally observed reduced reaction rate under cavity induced resonant vibrational strong light-matter coupling. We observe multiple resonances and obtain the thus far theoretically elusive but experimentally critical resonant feature for a single strongly coupled molecule undergoing the reaction. While we describe only a single mode and do not explicitly account for collective coupling or intermolecular interactions, the qualitative agreement with experimental measurements suggests that our conclusions can be largely abstracted towards the experimental realization. Specifically, we find that the cavity mode acts as mediator between different vibrational modes. In effect, vibrational energy localized in single bonds that are critical for the reaction is redistributed differently which ultimately inhibits the reaction.

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Section: Resultsmentioning

confidence: 90%

Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity

et al. 2022

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“…23,24 Recently, there has been an increasing interest in the properties of vibrational polariton systems resulting from the strong coupling of infrared (IR) cavity modes and ensembles of localized high-frequency vibrational modes in molecules in condensed phases. [25][26][27][28][29][30][31][32] The multilevel anharmonic spectrum of these vibrational modes implies that their accurate description should invoke more than two levels per emitter. Indeed, consideration of more realistic vibrational SC systems involving anharmonicities has been the subject of theoretical explorations, such as the use of single-molecule models to explain cavity-induced modifications to chemical reactivity, [33][34][35][36][37] as well as the use of many-molecule models a) Electronic mail: joelyuen@ucsd.edu; http://yuenzhougroup.ucsd.edu to explain non-linear response experiments.…”

Section: Introductionmentioning

confidence: 99%

Generalization of the Tavis–Cummings model for multi-level anharmonic systems

Campos-González-Angulo

Ribeiro

Yuen-Zhou

2021

New J. Phys.

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The interaction between anharmonic quantum emitters (e.g. molecular vibrations) and confined electromagnetic fields gives rise to quantum states with optical and chemical properties that are different from those of their precursors. The exploration of these properties has been typically constrained to the first excitation manifold, the harmonic approximation, ensembles of two-level systems [Tavis–Cummings (TC) model], or the anharmonic single-molecule case. The present work studies, for the first time, a collective ensemble of identical multi-level anharmonic emitters and their dipolar interaction with a photonic cavity mode, which is an exactly solvable many-body problem. The permutational properties of the system allow identifying symmetry classified submanifolds in the energy spectrum. Notably, in this approach, the number of particles, typically in the order of several millions, becomes only a parameter from the operational standpoint, and the size of the dimension of the matrices to diagonalize is independent of it. The formalism capabilities are illustrated by showing the energy spectrum structure, up to the third excitation manifold, and the calculation of the photon contents as a permutationally invariant quantity. Emphasis is placed on (a) the collective (superradiant) scalings of light–matter couplings and the various submanifolds of dark (subradiant) states with no counterpart in the single-molecule case, as well as (b) the delocalized modes containing more than one excitation per molecule with no equivalent in the TC model. We expect these findings to be applicable in the study of non-linear spectroscopy and chemistry of polaritons.

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“…This method has been previously applied ,− in cavity–vibration work, but our approach features simulations with all of the vibrationswith and without target vibrations, as well as interaction with multiple fringes as influenced by all of the untargeted vibrations. Standard TM programs, that we used previously, output the complex reflectance and transmission coefficients, as well as the fraction of light transmitted, reflected, and absorbed by the system, but they do not calculate the electric field within the etalon. E-field calculations were accomplished by adapting the programming of Burkhard and Hoke of the McGehee group to IR etalons.…”

Section: Resultsmentioning

confidence: 99%

“…Our method 20 of modeling cavity−vibration interactions and cavity-induced changes in vibration−vibration interactions within an etalon requires an accurate complex index of refraction of the subject solution vs wavelength. This, in turn, can be given in terms of the summed contribution of the system's vibrations, i.e., it is modeled as a sum of damped harmonic or Lorentz oscillators.…”

Section: Hexafluorophosphate Anion Pfmentioning

confidence: 99%

“…For comparison, the experimental integrated band intensity (by complex molar polarizability) of the CN triple-bond stretch of neat acetonitrile has been determined by Bertie and Lan and is 9.459 km/mol or 0.2239 0.25em D 2 normalÅ 2 normalu . So, the summed IR intensity of the degenerate ν 3 bands of PF 6 – is ∼146 times stronger than a band in pure acetonitrile which has been successfully used for strong vibrational coupling experiments …”

Section: Introductionmentioning

confidence: 99%

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Etalon-Assisted Determination of the Complex Index of Refraction of a Solution for the Study of Strong Cavity–Vibrational Coupling of PF₆^– in Acetonitrile

2023

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A new method is established using an etalon cavity to assist in the determination of the wavelength-dependent complex index of refraction of a solution throughout the mid-infrared range. The results are used to study the cavity−vibration polaritons of PF 6 − in acetonitrile. Mixed states are formed by placing solution inside a pair of parallel plate mirrors with a wavelength-scale spacing, i.e., within an etalon, such that there are cavity states that are angle-tuned into resonance with the strong P−F vibrations. The dominant ν 3 vibrations of PF 6 − consist of nearly triply degenerate oscillations of the partial-positively charged phosphorous against antisymmetric concerted motions of different sets of fluorine atoms with partial negative charges. These vibrations are dominant even though the solute is 29 times less concentrated than the solvent on a molar basis. The first part of the paper describes the method of determining the complex index of refraction of the solution from a combination of etalon transmission maxima and the attenuated total reflection (ATR) absorption spectrum of the solution. The results are presented as an analytical function including a sum of 37 vibrational contributions. Absolute integrated isolated band intensities were determined to be 463 ± 4, 462 ± 7, and 266 ± 4 km/mol for the three ν 3 PF 6 − vibrations at 841.4, 847.4, and 854.0 cm −1 , respectively, which sum to 1191 ± 9 km/mol for the ν 3 band. Then, the results are used to simulate the measured etalon transmission using the transfer matrix (TM) method with and without the ν 3 target vibrations. The etalon transmission simulations reconstruct the position of cavity modes in the absence of target vibrations. They provide input data for the testing of simple quantum mechanical models for the interaction of vibrations with cavity modes and the interactions of vibrations with other vibrations within the molecule and between solute and solvent. The model shows that the nearly degenerate ν 3 vibrations interact with each other with a vibration− vibration coupling of 33 ± 5 cm −1 . This is comparable to the cavity−vibration coupling of 30.4 ± 2.9 cm −1 of the two strongest vibrations of PF 6 − .

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Changing Vibration Coupling Strengths of Liquid Acetonitrile with an Angle-Tuned Etalon

Cited by 6 publications

References 66 publications

Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity

Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity

Generalization of the Tavis–Cummings model for multi-level anharmonic systems

Etalon-Assisted Determination of the Complex Index of Refraction of a Solution for the Study of Strong Cavity–Vibrational Coupling of PF₆^– in Acetonitrile

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Changing Vibration Coupling Strengths of Liquid Acetonitrile with an Angle-Tuned Etalon

Cited by 6 publications

References 66 publications

Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity

Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity

Generalization of the Tavis–Cummings model for multi-level anharmonic systems

Etalon-Assisted Determination of the Complex Index of Refraction of a Solution for the Study of Strong Cavity–Vibrational Coupling of PF6– in Acetonitrile

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Etalon-Assisted Determination of the Complex Index of Refraction of a Solution for the Study of Strong Cavity–Vibrational Coupling of PF₆^– in Acetonitrile