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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

Chemical reaction involves C=O bond breaking.Benzaldehyde reacts with phenylhydrazine to give a hydrazone, demonstrating a chemical reaction in which C=O bond breaking is involved.
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f5: Chemical reaction involves C=O bond breaking.Benzaldehyde reacts with phenylhydrazine to give a hydrazone, demonstrating a chemical reaction in which C=O bond breaking is involved.

Mentions: The strong coupling of vibrational modes demonstrated here could have profound consequences for chemistry, as well as biochemistry. We have already shown that the rate and yield of a chemical reaction can be modified by strongly coupling an electronic excited state to the vacuum field6. In that case, the reaction involved a light-induced isomerization, a structural transformation of individual photochromic molecules, electronically strongly coupled in the optical regime. However, most chemistry is done in the ground state and starts by bond breaking and formation. Therefore the modification of bond strengths in the ground state by strong coupling to molecular vibrations could open many possibilities in chemical reactivity, catalysis and site-selective reactions. For instance, the optical resonance could be selectively tuned to the vibration of a bond targeted for dissociation. A reduction of the vibrational frequency through hybridization will most likely imply a weakening of the bond strength f, since . The ground-state energy landscape governing the chemistry may be significantly modified. As an example of important chemical functional groups, the carbonyls (C=O), coupled in this study, play a central role in amide bonding in peptides and as coordinating units in metalloenzymes, as ligands in organometallic and coordination complexes and as the active site in many industrial and pharmaceutical syntheses. For instance, the reaction between benzaldehyde with phenylhydrazine to give a hydrazone, shown in Fig. 5, involves the breaking of the (C=O) bond and therefore its rate and possibly yield could be modified by such bond weakening through strong coupling. Of course this approach is not limited to the carbonyl stretch; any IR active mode of a molecular functional group could be coupled to a light mode in the way shown here.


Coherent coupling of molecular resonators with a microcavity mode.

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

Chemical reaction involves C=O bond breaking.Benzaldehyde reacts with phenylhydrazine to give a hydrazone, demonstrating a chemical reaction in which C=O bond breaking is involved.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

f5: Chemical reaction involves C=O bond breaking.Benzaldehyde reacts with phenylhydrazine to give a hydrazone, demonstrating a chemical reaction in which C=O bond breaking is involved.
Mentions: The strong coupling of vibrational modes demonstrated here could have profound consequences for chemistry, as well as biochemistry. We have already shown that the rate and yield of a chemical reaction can be modified by strongly coupling an electronic excited state to the vacuum field6. In that case, the reaction involved a light-induced isomerization, a structural transformation of individual photochromic molecules, electronically strongly coupled in the optical regime. However, most chemistry is done in the ground state and starts by bond breaking and formation. Therefore the modification of bond strengths in the ground state by strong coupling to molecular vibrations could open many possibilities in chemical reactivity, catalysis and site-selective reactions. For instance, the optical resonance could be selectively tuned to the vibration of a bond targeted for dissociation. A reduction of the vibrational frequency through hybridization will most likely imply a weakening of the bond strength f, since . The ground-state energy landscape governing the chemistry may be significantly modified. As an example of important chemical functional groups, the carbonyls (C=O), coupled in this study, play a central role in amide bonding in peptides and as coordinating units in metalloenzymes, as ligands in organometallic and coordination complexes and as the active site in many industrial and pharmaceutical syntheses. For instance, the reaction between benzaldehyde with phenylhydrazine to give a hydrazone, shown in Fig. 5, involves the breaking of the (C=O) bond and therefore its rate and possibly yield could be modified by such bond weakening through strong coupling. Of course this approach is not limited to the carbonyl stretch; any IR active mode of a molecular functional group could be coupled to a light mode in the way shown here.

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