Comment on "Theoretical study of the NO 3 radical reaction with CH 2 ClBr, CH 2 ICl, CH 2 BrI, CHCl 2 Br, and CHClBr 2 " by I. Alkorta, J. M. C. Plane, J. Elguero, J. Z. Dávalos, A. U. Acuña and A. Saiz-Lopez, Phys. Chem. Chem. Phys. 2022, 24 , 14365.

This comment addresses a systematic error in the potential energy surfaces of the title reactions presented in the original article by Alkorta et al. The NO 3 radical has D 3h symmetry in the electronic ground state while the M08HX functional employed in the original article predicts an incorrect C 2v geometry and energy. By combining thermodynamic data for the OH + HNO 3 → H 2 O + NO 3 reaction with spectroscopic data and results from M08HX calculations on HNO 3 , H 2 O and the OH radical, the ground state NO 3 radical energy is estimated to be 37 kJ mol -1 lower than reported for the C 2v geometry.