Details

Autor(en) / Beteiligte

• Du, Matthew
• Ribeiro, Raphael F.
• Yuen-Zhou, Joel

Titel

Remote Control of Chemistry in Optical Cavities

Ist Teil von

• Chem, 2019-05, Vol.5 (5), p.1167-1181

Ort / Verlag

United States: Elsevier Inc

Erscheinungsjahr

2019

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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. [Display omitted] •Proposed quantum device employs optical cavities to enable remote control of chemistry•A molecule in one vessel affects the reactivity of a molecule in another vessel•Reaction efficiency can be enhanced by an order of magnitude For a given reaction, tuning rates or yields is often achieved by chemical modification. However, synthetic difficulties can preclude such a strategy. A quantum electrodynamical alternative involves carrying out the reaction inside an optical microcavity, where the energy levels of the confined electromagnetic fields can hybridize with those of contained molecules, thereby changing reactivity. Here, we theoretically design a remote control of chemistry by using optical cavities. We show that the photoisomerization efficiency of nitrous acid in one cavity is enhanced by increasing the photoexcitation of glyoxylic acid in another cavity. This non-local technique, aided by the formation of delocalized light-matter quantum states called polaritons, not only challenges the fundamental physical basis that the “catalyst” must bind the reactant but also presents a purification-friendly method where the “catalyst” is inherently separated from reactant and products. Traditionally, the catalyst binds to its substrate to enhance chemical reactivity. Here, we theoretically design an optical-cavity-based quantum device that allows the photoexcitation of a “remote catalyst” in one cavity to influence the photochemistry of reactant in another cavity. This non-local effect relies on strong light-matter interaction provided by the cavities. Applying the device to the isomerization of nitrous acid, we demonstrate that increasing the photoexcitation of the “catalyst” can boost reaction efficiency by an order of magnitude.