From Fig. , we can see the regions (blue) of θ and ϕ where ortho-or para-substituted intermediates are more stable than the meta-substituted isomer. For example, the most stable energy for the ortho-substituted complex is achieved when θ ≈ 75 • and ϕ ≈ 35 • , which is 6.4 kcal/mol lower in energy than the meta-substituted complex. The most stable energy for the para-substituted complex is achieved when θ ≈ 70 • and ϕ ≈ 80 • , which is 2.0 kcal/mol more stable compared to metasubstituted complex. When θ = 0 • for ê = Z or θ = 180 • for ê = -Z, the cavity polarization is along Z-direction, where the molecular dipole is nearly zero and the cavity modification diminishes, as expected. Room temperature thermal energy is k B T ≈ 0.58 kcal/mol, and for the case of bromination outside the cavity, the meta-substituted intermediate species is thermodynamically stable compared to the ortho-and para-species by roughly 2 and 5 kcal/mol, respectively (see Fig. ). Thus, these results suggest that by coupling the nitrobenzene molecule to an optical cavity, the preferred bromination sites can be tuned to either ortho-substituted or para-substituted, whereas outside the cavity, meta-substituted products dominate under standard conditions. As such, coupling to the cavity allows obtaining the "impossible products" (para-and ortho-substituted PhNO 2 -Br) outside the cavity.