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Coherent coupling of molecular resonators with a microcavity mode.

Shalabney A, George J, Hutchison J, Pupillo G, Genet C, Ebbesen TW - Nat Commun (2015)

Bottom Line: The optical hybridization of the electronic states in strongly coupled molecule-cavity systems have revealed unique properties, such as lasing, room temperature polariton condensation and the modification of excited electronic landscapes involved in molecular isomerization.This enables the enhancement of the collective Rabi-exchange rate with respect to the single-oscillator coupling strength.The possibility of inducing large shifts in the vibrational frequency of selected molecular bonds should have immediate consequences for chemistry.

View Article: PubMed Central - PubMed

Affiliation: ISIS &icFRC, University of Strasbourg and CNRS (UMR 7006), 67000 Strasbourg, France.

ABSTRACT
The optical hybridization of the electronic states in strongly coupled molecule-cavity systems have revealed unique properties, such as lasing, room temperature polariton condensation and the modification of excited electronic landscapes involved in molecular isomerization. Here we show that molecular vibrational modes of the electronic ground state can also be coherently coupled with a microcavity mode at room temperature, given the low vibrational thermal occupation factors associated with molecular vibrations, and the collective coupling of a large ensemble of molecules immersed within the cavity-mode volume. This enables the enhancement of the collective Rabi-exchange rate with respect to the single-oscillator coupling strength. The possibility of inducing large shifts in the vibrational frequency of selected molecular bonds should have immediate consequences for chemistry.

No MeSH data available.


Related in: MedlinePlus

Polymer vibrational spectrum.(a) Transmission spectrum of polyvinyl acetate (PVAc) thin layer deposited on a Ge substrate. The thickness of the film is about 2 μm and the measurement was performed at normal incidence. The measured transmission is normalized to free-space transmission. The black line fits the data modelling the polymer dispersion by ideal damped harmonic oscillators (see Supplementary Note 2). The inset shows the absorption band of PVAc due to the (C=O)-bond-stretching band around 1,740 cm−1 with the same fit (black line). (b) Chemical structure of a single PVAc monomer unit. (c) Three-dimensional structure of one PVAc monomer showing the (C=O) bond.
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f1: Polymer vibrational spectrum.(a) Transmission spectrum of polyvinyl acetate (PVAc) thin layer deposited on a Ge substrate. The thickness of the film is about 2 μm and the measurement was performed at normal incidence. The measured transmission is normalized to free-space transmission. The black line fits the data modelling the polymer dispersion by ideal damped harmonic oscillators (see Supplementary Note 2). The inset shows the absorption band of PVAc due to the (C=O)-bond-stretching band around 1,740 cm−1 with the same fit (black line). (b) Chemical structure of a single PVAc monomer unit. (c) Three-dimensional structure of one PVAc monomer showing the (C=O) bond.

Mentions: IR spectra associated with gas-phase molecules usually display features where rotational transitions are coupled to vibrational ones. The resulting well-known complexity of rovibrational molecular spectra leads to spectral components separated by wavenumbers <10 cm−1. Still, there are specific environments where molecules can display much simpler spectra from which it is possible to select and manipulate chosen vibrational normal modes. Polymeric phases are in this context particularly interesting to explore, since free rotations of molecular moieties are frozen-out and the excitation spectrum of the polymer is determined solely by electronic and vibrational contributions. One should also consider low-frequency vibrations of the polymer lattice itself. Yet, given the small wavenumbers for such lattice vibrations (less than ca. 100 cm−1) compared with the vibrations of individual bonds (ca. 1,000 cm−1), the two classes of motions can be clearly separated1. In this regime therefore, vibrational spectra of polymers display normal-mode transitions sufficiently isolated from the background to be tuned properly to a given cavity resonance, as presented in Fig. 1.


Coherent coupling of molecular resonators with a microcavity mode.

Shalabney A, George J, Hutchison J, Pupillo G, Genet C, Ebbesen TW - Nat Commun (2015)

Polymer vibrational spectrum.(a) Transmission spectrum of polyvinyl acetate (PVAc) thin layer deposited on a Ge substrate. The thickness of the film is about 2 μm and the measurement was performed at normal incidence. The measured transmission is normalized to free-space transmission. The black line fits the data modelling the polymer dispersion by ideal damped harmonic oscillators (see Supplementary Note 2). The inset shows the absorption band of PVAc due to the (C=O)-bond-stretching band around 1,740 cm−1 with the same fit (black line). (b) Chemical structure of a single PVAc monomer unit. (c) Three-dimensional structure of one PVAc monomer showing the (C=O) bond.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4308833&req=5

f1: Polymer vibrational spectrum.(a) Transmission spectrum of polyvinyl acetate (PVAc) thin layer deposited on a Ge substrate. The thickness of the film is about 2 μm and the measurement was performed at normal incidence. The measured transmission is normalized to free-space transmission. The black line fits the data modelling the polymer dispersion by ideal damped harmonic oscillators (see Supplementary Note 2). The inset shows the absorption band of PVAc due to the (C=O)-bond-stretching band around 1,740 cm−1 with the same fit (black line). (b) Chemical structure of a single PVAc monomer unit. (c) Three-dimensional structure of one PVAc monomer showing the (C=O) bond.
Mentions: IR spectra associated with gas-phase molecules usually display features where rotational transitions are coupled to vibrational ones. The resulting well-known complexity of rovibrational molecular spectra leads to spectral components separated by wavenumbers <10 cm−1. Still, there are specific environments where molecules can display much simpler spectra from which it is possible to select and manipulate chosen vibrational normal modes. Polymeric phases are in this context particularly interesting to explore, since free rotations of molecular moieties are frozen-out and the excitation spectrum of the polymer is determined solely by electronic and vibrational contributions. One should also consider low-frequency vibrations of the polymer lattice itself. Yet, given the small wavenumbers for such lattice vibrations (less than ca. 100 cm−1) compared with the vibrations of individual bonds (ca. 1,000 cm−1), the two classes of motions can be clearly separated1. In this regime therefore, vibrational spectra of polymers display normal-mode transitions sufficiently isolated from the background to be tuned properly to a given cavity resonance, as presented in Fig. 1.

Bottom Line: The optical hybridization of the electronic states in strongly coupled molecule-cavity systems have revealed unique properties, such as lasing, room temperature polariton condensation and the modification of excited electronic landscapes involved in molecular isomerization.This enables the enhancement of the collective Rabi-exchange rate with respect to the single-oscillator coupling strength.The possibility of inducing large shifts in the vibrational frequency of selected molecular bonds should have immediate consequences for chemistry.

View Article: PubMed Central - PubMed

Affiliation: ISIS &icFRC, University of Strasbourg and CNRS (UMR 7006), 67000 Strasbourg, France.

ABSTRACT
The optical hybridization of the electronic states in strongly coupled molecule-cavity systems have revealed unique properties, such as lasing, room temperature polariton condensation and the modification of excited electronic landscapes involved in molecular isomerization. Here we show that molecular vibrational modes of the electronic ground state can also be coherently coupled with a microcavity mode at room temperature, given the low vibrational thermal occupation factors associated with molecular vibrations, and the collective coupling of a large ensemble of molecules immersed within the cavity-mode volume. This enables the enhancement of the collective Rabi-exchange rate with respect to the single-oscillator coupling strength. The possibility of inducing large shifts in the vibrational frequency of selected molecular bonds should have immediate consequences for chemistry.

No MeSH data available.


Related in: MedlinePlus