Accurate calculations on excited states: new theories applied to the –OX, –XO, and –XO 2 (X=Cl and Br) chromophores and implications for stratospheric bromine chemistry

Abstract

Electronic excitation energies are determined using single-reference based theories derived from response equations involving perturbation theory and coupled-cluster theory. These methods are applied to the singlet manifold of excited electronic states of the HClO, HBrO, HOClO, HOBrO, HClO 2, and HBrO 2 molecules. Vertical excitation energies (VEEs) for the lowest symmetry unique triplet states are also computed using coupled-cluster theory. Both the singlet and triplet coupled-cluster VEEs are found to be in excellent agreement with experiment for HOBr and HOCl. The reliability of the various perturbation theory approaches is assessed by comparison to the linear response coupled-cluster method, and the CIS(D3) approach is found to perform the best, on average. In order to obtain reliable VEEs for these molecules, CIS(D3) is the recommended approach, unless excited state non-dynamical electron correlation is significant, in which case the recently proposed CIS(D 0) technique may perform better, on average. For both the HClO 2 and HBrO 2 molecules, it is found that the lowest singlet excited electronic state occurs at too high an energy for it to be accessible from solar radiation in the lower stratosphere. The stratospheric chemistry implications of this, especially for bromine chemistry are discussed. It is suggested that YBrO 2 molecules may in fact be the only stable stratospheric bromine reservoir species under light conditions.