Non-Polaritonic Effects in Cavity-Modified Photochemistry.

Strong coupling of molecules to vacuum fields is widely reported to lead to modified chemical properties such as reaction rates. However, some recent attempts to reproduce infrared strong coupling results have not been successful, suggesting that factors other than strong coupling may sometimes be involved. In the first vacuum-modified chemistry experiment, changes to a molecular photoisomerization process in the ultraviolet-visible spectral range are attributed to strong coupling of the molecules to visible light. Here, this process is re-examined, finding significant variations in photoisomerization rates consistent with the original work. However, there is no evidence that these changes need to be attributed to strong coupling. Instead, it is suggested that the photoisomerization rates involved are most strongly influenced by the absorption of ultraviolet radiation in the cavity. These results indicate that care must be taken to rule out non-polaritonic effects before invoking strong coupling to explain any changes of properties arising in cavity-based experiments.

Origin of an Anticrossing between a Leaky Photonic Mode and an Epsilon-Near-Zero Point of Silver.

Strong light-matter coupling hybridizes light and matter to form states known as polaritons, which give rise to a characteristic anticrossing signature in dispersion plots. Here, we identify conditions under which an anticrossing can occur in the absence of strong coupling. We study planar silver/dielectric structures and find that, around the epsilon-near-zero point in silver, the impedance matching between the silver and dielectric layers gives rise to an anticrossing. Our work shows that care must be taken to ensure that anticrossing arising from impedance matching is not misattributed to strong coupling.

Single vs double anti-crossing in the strong coupling between surface plasmons and molecular excitons.

Strong coupling between surface plasmons and molecular excitons may lead to the formation of new hybrid states-polaritons-that are part light and part matter in character. A key signature of this strong coupling is an anti-crossing of the exciton and surface plasmon modes on a dispersion diagram. In a recent report on strong coupling between the plasmon modes of a small silver nano-rod and a molecular dye, it was shown that when the oscillator strength of the exciton is large enough, an additional anti-crossing feature may arise in the spectral region where the real part of the permittivity of the excitonic material is zero. However, the physics behind this double anti-crossing feature is still unclear. Here, we make use of extensive transfer matrix simulations to explore this phenomenon. We show that for low oscillator strengths of the excitonic resonance, there is a single anti-crossing arising from strong coupling between the surface plasmon and the excitonic resonance, which is associated with the formation of upper and lower plasmon-exciton polaritons. As the oscillator strength is increased, we find that a new mode emerges between these upper and lower polariton states and show that this new mode is an excitonic surface mode. Our study also features an exploration of the role played by the orientation of the excitonic dipole moment and the relationship between the modes we observe and the transverse and longitudinal resonances associated with the excitonic response. We also investigate why this type of double splitting is rarely observed in experiments.

A New Signature for Strong Light-Matter Coupling Using Spectroscopic Ellipsometry.

Light-matter interactions can occur when an ensemble of molecular resonators is placed in a confined electromagnetic field. In the strong coupling regime the rapid exchange of energy between the molecules and the electromagnetic field results in the emergence of hybrid light-matter states called polaritons. Multiple criteria exist to define the strong coupling regime, usually by comparing the splitting of the polariton bands with the line widths of the uncoupled modes. Here, we highlight the limitations of these criteria and study strong coupling using spectroscopic ellipsometry, a commonly used optical characterization technique. We identify a new signature of strong coupling in ellipsometric phase spectra. The combination of ellipsometric amplitude and phase spectra yields a distinct topological feature that we suggest could serve as a new criterion for strong coupling. Our results introduce the idea of ellipsometric topology and could provide further insight into the transition from the weak to strong coupling regime.