Cavity-Modulated Proton Transfer Reactions

Proton transfer is ubiquitous in
many fundamental chemical and
biological processes, and the ability to modulate and control the
proton transfer rate would have a major impact on numerous quantum
technological advances. One possibility to modulate the reaction rate
of proton transfer processes is given by exploiting the strong light-matter
coupling of chemical systems inside optical or nanoplasmonic cavities.
In this work, we investigate the proton transfer reactions in the
prototype malonaldehyde and Z-3-amino-propenal (aminopropenal)
molecules using different quantum electrodynamics methods, in particular,
quantum electrodynamics coupled cluster theory and quantum electrodynamical
density functional theory. Depending on the cavity mode polarization
direction, we show that the optical cavity can increase the reaction
energy barrier by 10–20% or decrease the reaction barrier by
∼5%. By using first-principles methods, this work establishes
strong light-matter coupling as a viable and practical route to alter
and catalyze proton transfer reactions.