Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 35858927.
- Also identified by DOI 10.1038/s41467-022-31703-8 and PMC identifier 9300737.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
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 <sup>13</sup>CO<sub>2</sub> solute in a <sup>12</sup>CO<sub>2</sub> 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.