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Abstract
Coupling vibrational transitions to resonant optical modes creates vibrational polaritons
shifted from the uncoupled molecular resonances and provides a convenient way to modify
the energetics of molecular vibrations. This approach is a viable method to explore
controlling chemical reactivity. In this work, we report pump–probe infrared spectroscopy
of the cavity-coupled C–O stretching band of W(CO)
6 and the direct measurement of the lifetime of a vibration-cavity polariton. The upper
polariton relaxes 10 times more quickly than the uncoupled vibrational mode. Tuning
the polariton energy changes the polariton transient spectra and relaxation times.
We also observe quantum beats, so-called vacuum Rabi oscillations, between the upper
and lower vibration-cavity polaritons. In addition to establishing that coupling to
an optical cavity modifies the energy-transfer dynamics of the coupled molecules,
this work points out the possibility of systematic and predictive modification of
the excited-state kinetics of vibration-cavity polariton systems.
Abstract
Vibration-cavity polaritons are mixed states produced by strong coupling between a
vibrational mode and an optical cavity. Here, the authors show that these polaritons
can coherently exchange energy and exhibit drastically altered transient spectra and
dynamics compared to uncoupled vibrations.
In this review we look at the concepts and state-of-the-art concerning the strong coupling of surface plasmon-polariton modes to states associated with quantum emitters such as excitons in J-aggregates, dye molecules and quantum dots. We explore the phenomenon of strong coupling with reference to a number of examples involving electromagnetic fields and matter. We then provide a concise description of the relevant background physics of surface plasmon polaritons. An extensive overview of the historical background and a detailed discussion of more recent relevant experimental advances concerning strong coupling between surface plasmon polaritons and quantum emitters is then presented. Three conceptual frameworks are then discussed and compared in depth: classical, semi-classical and fully quantum mechanical; these theoretical frameworks will have relevance to strong coupling beyond that involving surface plasmon polaritons. We conclude our review with a perspective on the future of this rapidly emerging field, one we are sure will grow to encompass more intriguing physics and will develop in scope to be of relevance to other areas of science.
Intra-molecular vibrational motions can be described as a superposition of simple harmonic vibrations, so called molecular normal modes. For each of these modes, the atoms vibrate in specific directions that correspond to the observable vibrational transitions measured in infrared (IR) spectroscopy. The relatively high frequencies of molecular vibrational transitions ω ν , fixed by the bond strength f (typically of the order of 103 N m−1) and the tiny atomic masses involved in the vibrations, immediately lead to two important features. First, it is possible to perform direct resonant dipolar coupling by engineering micro-scaled cavities with a fundamental mode ω c tuned to the molecular vibrational transitions. Then, as a consequence of their high frequencies in the IR regime, vibrational resonances are characterized by small thermal occupation factors , even at room temperature. This means that such molecular normal modes are in their ground state, allowing coherent light–matter coupling in a straightforward manner. In the following, we demonstrate the coherent coupling between molecular vibrational transitions and an optical mode of a microcavity, leading to the possibility to swap, at room temperature, excitations coherently between the molecular oscillators and the optical mode. To do so, we have exploited two crucial features offered by polymers. First, the possibility to have an isolated, practically homogeneous, spectral signal associated to a specific vibrational molecular normal mode. Second, the capacity offered through the bulky extension of the polymer film inserted in a Fabry–Perot microcavity to have within a volume of strong optical confinement (that is, the coherence volume of the cavity mode) a large number of resonators. The colocalization of the optical and mechanical modes induces a collective enhancement of the resonant coupling rate between the vibrational resonators and the cavity mode, reaching the regime of strong coherent coupling. In other words, a macroscopic coherent mechanical mode is now generated by strong coupling. Results Hamiltonian description 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 >k B T/ħ, thermal decoherence can be neglected over more than one vibrational period. Thus, essentially due to the extremely tiny effective mass involved in the mechanical stretching mode of the (C=O) bond, coherent coupling is achieved at room temperature. In addition, the high mechanical product Q v ·ω v /2π holds promises in the context of transient spectroscopy. Indeed, while our discussion was here limited to the electronic ground state and first vibrational transition, one can envision to actually pump transiently the vibrational manifold. This might lead to inverted population dynamics in connection with polariton vibrational lasing21. Finally, because it involves dressed collective modes through the colocalization of the cavity field and the vibrational modes, large coupling rates with ratios Ω R/κ close to 1 can be reached. This could lead to nonlinear behaviour in the IR regime similar to that recently demonstrated for polariton Bose–Einstein condensation22 23 in the optical regime. 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. The possibility of modifying chemical reaction rates, as described above, seems plausible based on several earlier experiments where bulk properties were modified by strong coupling, such as the already cited photochemical reaction, work-function and the ground-state energy6 24 25. However, the actual mechanism of how strong coupling modifies the molecular material properties is still not clear, and it might be counter-intuitive that the collective coupling induced in such systems will affect the properties of individual molecules. Further theory is indeed needed on such topics that can handle the complexity of strongly coupled molecular systems to be able to fully understand the potential of light–matter strong coupling for molecular science. Author contributions All authors contributed to all aspects of this work. Additional information How to cite this article: Shalabney, A. et al. Coherent coupling of molecular resonators with a microcavity mode. Nat. Commun. 6:5981 doi: 10.1038/ncomms6981 (2015). Supplementary Material Supplementary Information Supplementary Figure 1, Supplementary Table 1, Supplementary Notes 1-4, and Supplementary References
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Vibration-cavity polaritons are mixed states produced by strong coupling between a
vibrational mode and an optical cavity. Here, the authors show that these polaritons
can coherently exchange energy and exhibit drastically altered transient spectra and
dynamics compared to uncoupled vibrations.
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