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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.
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Resonantly enhanced polariton wave mixing and parametric instability in a Floquet medium
We introduce a new theoretical approach for analyzing pump and probe experiments in non-linear systems of optical phonons. In our approach, the effect of coherently pumped polaritons is modeled as providing time-periodic modulation of the system parameters. Within this framework, propagation of the probe pulse is described by the Floquet version of Maxwell’s equations and leads to phenomena such as frequency mixing and resonant parametric production of polariton pairs. We analyze light reflection from a slab of insulating material with a strongly excited phonon-polariton mode and obtain analytic expressions for the frequency-dependent reflection coefficient for the probe pulse. Our results are in agreement with recent experiments by Cartella et al. [Proc. Natl. Acad. Sci. U. S. A. 115, 12148 (2018)], which demonstrated light amplification in a resonantly excited SiC insulator. We show that, beyond a critical pumping strength, such systems should exhibit Floquet parametric instability, which corresponds to resonant scattering of pump polaritons into pairs of finite momentum polaritons. We find that the parametric instability should be achievable in SiC using current experimental techniques and discuss its signatures, including the non-analytic frequency dependence of the reflection coefficient and the probe pulse afterglow. We discuss possible applications of the parametric instability phenomenon and suggest that similar types of instabilities can be present in other photoexcited non-linear systems.
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- Award ID(s):
- 2012023
- PAR ID:
- 10593522
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 156
- Issue:
- 17
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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