Failures and limitations of quantum chemistry for two key problems in the atmospheric chemistry of peroxy radicals

Quantum chemical calculations have obtained significant and useful information about chemical reactions relevant to atmospheric chemistry. This article reviews two problems for which it would seem that such calculations could readily provide a great deal of helpful information, but for which that potential has not been fully realized. The first is the formation of alkylnitrates (RONO2) from the reaction of peroxy radicals (ROO center dot) with NO. Several studies of this process have been carried out, but most clearly yielded unphysical results due to methodological pitfalls. The one study which appears valid [Zhao, Y., Houk, K.N., Olson, L.P., 2004. Mechanisms of peroxynitrous acid and methyl peroxynitrite, ROONO (R = H, Me), rearrangements: a conformation-dependent homolytic dissociation. Journal of Physical Chemistry A 108, 5864-5871] suggests an indirect route between ROONO and RONO2, and implies that statistical rate theory will be insufficient to understand the yields of RONO2, The second problem discussed here is the competition between radical production and disproportionation in the self-reaction of organic peroxy radicals, for which only one quantum chemical study has found a plausible mechanism connecting reactants with products. (c) 2007 Elsevier Ltd. All rights reserved.