On the S <sub>N</sub> 2 reactions modified in vibrational strong coupling experiments: reaction mechanisms and vibrational mode assignments
Clàudia Climent, Johannes Feist
Abstract
2@Si reactions, obtaining in both cases a triple-well PES where the rate-determining step is due to the Si-C and Si-O bond cleavage. Secondly, we characterize in detail the normal modes of vibration of the reactants. In the VSC experiments, reaction rates were modified only when specific vibrations of the reactants were coupled to a cavity mode. We find that these vibrations are highly mixed among the different fragments of the reactants leading to a completely new assignment of the IR peaks coupled to cavity modes in the original experimental works. Our results are fundamental for the interpretation of the VSC experiments given that in the absence of a theory explaining these results, the current phenomenological understanding relies on the assignment of the character of the vibrational IR peaks.