Ab Initio MRD-CI Study of the Electronic Spectrum of BrNO2 and Photofragmentation

Abstract

Multi reference configuration interaction, MRD-CI, methods with the cc-pVDZ+sp and cc-pVTZ+sp basis sets were employed to determine the low-lying singlet and triplet electronic states of nitryl bromide, BrNO 2 . The calculations predict two very strong transitions, 3 1 A 1 ← X 1 A 1 and 3 1 B 2 ← X 1 A 1 , at 6.15 and 7.27 eV, respectively. At wavelengths that are atmospherically relevant to the BrNO 2 photolysis, 1 1 B 2 and 1 1 B 1 singlet states with vertical transition energies of 3.43 and 3.85 eV, respectively, are computed. The corresponding triplet states are lower in energy by 0.27 and 0.36 eV, respectively. Both singlet and triplet states are found to be highly repulsive along the Br-N coordinate and they dissociate to the ground-state fragments Br and NO 2 . The comparison between the first singlet excited state of BrNO 2 and ClNO 2 demonstrates that the transition is red-shifted by 80 nm from ClNO 2 upon replacement of chlorine by bromine. Furthermore, the most intense transition 3 1 A 1 ← X 1 A 1 of BrNO 2 has a 0.9 eV lower energy than that of ClNO 2 . These energy differences can be explained by the large halogen character of the orbitals involved in the electron excitations.