Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping

Li, Tao E.; Nitzan, Abraham; Subotnik, Joseph E.

doi:10.1038/s41467-022-31703-8

Title: Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping

Journal Article · 19 July 2022 · Nature Communications

DOI: https://doi.org/10.1038/s41467-022-31703-8 · OSTI ID:1876930

; Nitzan, Abraham;

Abstract Selectively exciting target molecules to high vibrational states is inefficient in the liquid phase, which restricts the use of IR pumping to catalyze ground-state chemical reactions. Here, we demonstrate that this inefficiency can sometimes be solved by confining the liquid to an optical cavity under vibrational strong coupling conditions. For a liquid solution of ¹³ CO ₂ solute in a ¹² CO ₂ solvent, cavity molecular dynamics simulations show that exciting a polariton (hybrid light-matter state) of the solvent with an intense laser pulse, under suitable resonant conditions, may lead to a very strong (>3 quanta) and ultrafast (<1 ps) excitation of the solute, even though the solvent ends up being barely excited. By contrast, outside a cavity the same input pulse fluence can excite the solute by only half a vibrational quantum and the selectivity of excitation is low. Our finding is robust under different cavity volumes, which may lead to observable cavity enhancement on IR photochemical reactions in Fabry–Pérot cavities.

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Research Organization:: Univ. of Pennsylvania, Philadelphia, PA (United States); University of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: U.S. National Science Foundation; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0019397

OSTI ID:: 1876930

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 13; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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Title: Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping

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