Cavity Quantum Electrodynamics Enables para- and ortho- Bromination of Nitrobenzene

Coupling molecules to a quantized radiation field inside an optical cavity has shown great promise to modify chemical reactivity. While most ongo- ing work is leveraging resonance effects between the molecular transitions and the frequency of the cavity, the ground state can also be modified through non-resonant effects dominated by dipole self-energy contributions. In this work, we predict that the ground state selectivity of the bromina- tion of nitrobenzene can be fundamentally changed by strongly coupling to the cavity, generating the ortho- or para-substituted products. These are products that one does not obtain from the same reaction outside the cavity. We use the recently developed ab initio polariton chemistry approach and theoretically compute the relative energies of the cationic Wheland intermediates, which in- dicates the kinetically preferred bromination site. We have further provided an analysis of the ground state electron density difference between inside and outside cavity, and we demonstrate how coupling to the cavity can change the charge distribution which leads to different bromination sites.