Issue 23, 2021

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

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Mar 2021
Accepted
02 May 2021
First published
06 May 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 8088-8095

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

B. Gu, S. M. Cavaletto, D. R. Nascimento, M. Khalil, N. Govind and S. Mukamel, Chem. Sci., 2021, 12, 8088 DOI: 10.1039/D1SC01774H

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