Impact of Cavity Length Non-uniformity on Reaction Rate Extraction in Strong Coupling Experiments

Area of Science:

• Chemical Physics
• Spectroscopy
• Physical Chemistry

Background:

• Vibrational strong coupling (VSC) studies report altered chemical phenomena, but results are often met with skepticism.
• Irreproducible findings and a lack of theoretical frameworks hinder VSC research acceptance.

Purpose of the Study:

• To identify and characterize a UV-vis measurement artifact affecting optical microcavity studies.
• To propose a correction method for accurate chemical rate determination in VSC experiments.

Main Methods:

• Utilized the Transfer Matrix (TM) method to model and predict artifact behavior.
• Performed experimental validation of the predicted artifact.
• Developed a correction technique involving an effective molar absorption coefficient.

Main Results:

• Identified a UV-vis artifact that distorts absorption peaks, amplitudes, and calculated reaction rates.
• Successfully predicted and experimentally confirmed the artifact's characteristics.
• Demonstrated a correction method to improve measurement accuracy.

Conclusions:

• The identified artifact has significant implications for existing cavity-modified chemistry research.
• This work establishes best practices for future investigations in VSC and optical microcavities.
• Correcting for this artifact enhances the reliability and reproducibility of VSC experiments.