Comment on “Theoretical study of the NO3 radical reaction with CH2ClBr, CH2ICl, CH2BrI, CHCl2Br, and CHClBr2” 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

Abstract

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 NO₃ 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 + HNO₃ → H₂O + NO₃ reaction with spectroscopic data and results from M08HX calculations on HNO₃, H₂O and the OH radical, the ground state NO₃ radical energy is estimated to be 37 kJ mol⁻¹ lower than reported for the C_2v geometry.