4.8 Article

Remote Control of Chemistry in Optical Cavities

Journal

CHEM
Volume 5, Issue 5, Pages 1167-1181

Publisher

CELL PRESS
DOI: 10.1016/j.chempr.2019.02.009

Keywords

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Funding

  1. UCSD CRES
  2. AFOSR [FA9550-18-1-0289]
  3. US Department of Energy, Office of Science, Basic Energy Sciences, CPIMS Program under Early Career Research Program [DE-SC0019188]
  4. U.S. Department of Energy (DOE) [DE-SC0019188] Funding Source: U.S. Department of Energy (DOE)

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Manipulation of chemical reactivity often involves changing reagents or environmental conditions. Alternatively, strong coupling between light and matter offers ways to tunably hybridize their physicochemical properties and thereby change reaction dynamics without synthetic modifications to starting materials. Here, we theoretically design a polaritonic (hybrid photonic-molecular) device that supports ultrafast tuning of reaction yields even when the catalyst and reactant are spatially separated across several optical wavelengths. We demonstrate how photoexcitation of the remote catalyst in an optical microcavity can control the photochemistry of the reactant in another microcavity. Harnessing the delocalization that arises from strong cavity-molecule coupling of the spatially separated compounds, this intriguing phenomenon is shown for the infrared-induced cis -> trans conformational isomerization of nitrous acid. Indeed, increasing the excited-state population of the remote catalyst can enhance isomerization efficiency by an order of magnitude. The theoretical proposal herein is generalizable to other reactions and thus introduces a versatile tool to control photochemistry.

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