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

Autor: Gu B; Department of Chemistry and Department of Physics & Astronomy, University of California Irvine CA 92697 USA smukamel@uci.edu., Cavaletto SM; Department of Chemistry and Department of Physics & Astronomy, University of California Irvine CA 92697 USA smukamel@uci.edu., Nascimento DR; Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory Richland WA 99352 USA., Khalil M; Department of Chemistry, University of Washington Seattle WA USA., Govind N; Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory Richland WA 99352 USA., Mukamel S; Department of Chemistry and Department of Physics & Astronomy, University of California Irvine CA 92697 USA smukamel@uci.edu.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2021 May 06; Vol. 12 (23), pp. 8088-8095. Date of Electronic Publication: 2021 May 06.
DOI: 10.1039/d1sc01774h
Abstrakt: 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.
Competing Interests: There are no conflicts to declare.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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