We want to check whether the rates of basic chemical reactions: proton and electron transfer can be changed by placing the molecules in appropriately designed photonic cavities.This is a central problem in a new research area, dubbed "Polaritonic chemistry", and intensely developed in the last years. The molecules are placed in so-called photonic cavities: small volume elements of micro- or nanometer dimensions, such as two closely spaced parallel mirrors, which support only certain radiation wavelengths. If a wavelength corresponds to the energy of a molecular transition, efficient mixing of radiation and matter states occurs. Such interaction is called strong coupling, and the resulting 1:1 hybrid-matter state is named a polariton. Several works claimed ed that the chemistry of polaritonic systems may be completely different than the chemistry of "normal" molecules.

  

We plan to study modifications of reactivity in both ground and electronically excited states. For this purpose, two different methodologies will be tested. In the first approach, we want to  induce nanocavity-induced shifts of the energies of electronic transitions of the reactants or products. The molecules will be placed in nanocavities tuned to the frequencies corresponding to electronic transitions in the reactant (absorption and emission, respectively) and to the emission of the photoproduct. One can expect that tuning to the reactant should result in slowing down of the reaction, since the energy of the initial state will be lowered compared to molecules outside (or in a detuned) nanocavity. The opposite effect should be observed whole tuning to the reactant transition.

The other approach will be based on creating vibrational polaritons in order to affect the multidimensional reaction path.In this way, reactivity could be affected in both electronic ground and excited states.

  

Our studies should also shed light on the influence of nanocavities on (i) hydrogen bond properties, (ii) photostability, (iii) Raman scattering, (iv) photophysics, and (v) magnetic circular dichroism (MCD) spectra.

  

The compounds selected for investigations will include proton- or electron-transferring molecules of which the ground and/or electronically excited state reactivities under "normal" conditions have been well characterized. These molecules have been studied before in our laboratory; most of them have also been synthesized by us. The project will include participation of a synthetic team, not only to ensure the delivery of molecules, but to enable structural modifications as the work progresses.