Manipulating valence and core electronic excitations of a transition-metal complex using UV/Vis and X-ray cavities

We demonstrate how optical cavities can be exploited to control both valence- and core-excitations in a prototypical model transition metal complex, ferricyanide ([Fe(iii)(CN)(6)](3−)), in an aqueous environment. The spectroscopic signatures of hybrid light-matter polariton states are revealed in UV/Vis and X-ray absorption, and stimulated X-ray Raman signals. In an UV/Vis cavity, the absorption spectrum exhibits the single-polariton states arising from the cavity photon mode coupling to both resonant and off-resonant valence-excited states. We further show that nonlinear stimulated X-ray Raman signals can selectively probe the bipolariton states via cavity-modified Fe core-excited states. This unveils the correlation between valence polaritons and dressed core-excitations. In an X-ray cavity, core-polaritons are generated and their correlations with the bare valence-excitations appear in the linear and nonlinear X-ray spectra.