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Title: 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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Department of Chemistry and Department of Physics & Astronomy, University of California, Irvine, USA
  2. Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, USA
  3. Department of Chemistry, University of Washington, Seattle, USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1782956
Alternate Identifier(s):
OSTI ID: 1782480
Report Number(s):
PNNL-SA-160949
Journal ID: ISSN 2041-6520; CSHCBM
Grant/Contract Number:  
FG02-04ER15571; SC0019277; KC-030103172684; AC05-76RL1830; AC05-76RL01830; CHE-1953045
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 12 Journal Issue: 23; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gu, Bing, Cavaletto, Stefano M., Nascimento, Daniel R., Khalil, Munira, Govind, Niranjan, and Mukamel, Shaul. Manipulating valence and core electronic excitations of a transition-metal complex using UV/Vis and X-ray cavities. United Kingdom: N. p., 2021. Web. doi:10.1039/D1SC01774H.
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Gu, Bing, Cavaletto, Stefano M., Nascimento, Daniel R., Khalil, Munira, Govind, Niranjan, & Mukamel, Shaul. Manipulating valence and core electronic excitations of a transition-metal complex using UV/Vis and X-ray cavities. United Kingdom. https://doi.org/10.1039/D1SC01774H
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Gu, Bing, Cavaletto, Stefano M., Nascimento, Daniel R., Khalil, Munira, Govind, Niranjan, and Mukamel, Shaul. Wed . "Manipulating valence and core electronic excitations of a transition-metal complex using UV/Vis and X-ray cavities". United Kingdom. https://doi.org/10.1039/D1SC01774H.
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@article{osti_1782956,
title = {Manipulating valence and core electronic excitations of a transition-metal complex using UV/Vis and X-ray cavities},
author = {Gu, Bing and Cavaletto, Stefano M. and Nascimento, Daniel R. and Khalil, Munira and Govind, Niranjan and Mukamel, Shaul},
abstractNote = {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.},
doi = {10.1039/D1SC01774H},
journal = {Chemical Science},
number = 23,
volume = 12,
place = {United Kingdom},
year = {Wed Jun 16 00:00:00 EDT 2021},
month = {Wed Jun 16 00:00:00 EDT 2021}
}
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https://doi.org/10.1039/D1SC01774H
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