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Photochemistry studied with ab initio orbital‐correlation and state‐correlation plots: Classic cyclobutene ring opening, and the reaction of N2 with photoexcited O2

Pericyclic reaction theory arose from ideas presented in 1965, based on orbital‐energy correlation diagrams (Woodward and Hoffmann) and state‐energy correlation diagrams (Longuet‐Higgins and Abrahamson). Here we have used ab initio complete‐active‐space self‐consistent field (CASSCF) calculations to generate such diagrams. First we present diagrams for the classic case of cyclobutene ring opening, to demonstrate agreement between the CASSCF results and the classic diagrams of both Woodward/Hoffmann and Longuet‐Higgins/Abrahamson. Then we present diagrams for the more difficult cases of N2 + photoexcited O2, to produce either 2 NO or NNO + O. These N2 + O2 cases feature significant electron reorganization, for which elementary pencil‐and‐paper diagrams are less accurate. Finally, the benefits and limitations of such diagrams for predicting photochemistry are briefly discussed. © 2007 Wiley Periodicals, Inc. J Comput Chem 2008