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We introduce a prototypical model for cavity polaritonic control of ultracoldphotochemistry by considering the resonant vibrational strong coupling of arubidium dimer to a terahertz cavity. We demonstrate that at avoided crossingsbetween a vibrational excitation and the vacuum photon absorption, theresulting polaritonic states between the molecule and photons can efficientlycontrol the molecular vibrational Franck-Condon (FC) factors. Due to theentanglement between light and matter, FC factor is transferred from onepolaritonic branch to other, leading to a polariton with a substantiallyenhanced FC factor. Utilizing this polariton state for photoassociation resultsin the enhanced formation of ultracold molecules. This work suggests a path tocontrolling photoassociation with cavity vacuum fields, and lays the ground forthe emerging subfield of polaritonic ultracold chemistry.

Polaritonic ultracold reactions: cavity controlled molecular photoassociation