Manipulating valence and core electronic excitations of a transition-metal complex using UV/Vis and X-ray cavities |
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| Authors: | Bing Gu Stefano M Cavaletto Daniel R Nascimento Munira Khalil Niranjan Govind Shaul Mukamel |
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| Institution: | Department of Chemistry and Department of Physics & Astronomy, University of California, Irvine CA 92697 USA.; Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA ; Department of Chemistry, University of Washington, Seattle WA USA |
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| Abstract: | 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.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. |
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