The ground-, (1)(pipi*)-, and (3)(pipi*)-state potential-energy surfaces of 1,2-cyclononadiene and isomeric C(9)H(14) species, as well as 1-methyl-1,2-cyclononadiene and isomeric C(10)H(16) species were all mapped using CASSCF and the 6-31G(d) basis set. Theoretical results were found to be in good agreement with the available experimental observations for both 1,2-cyclononadiene and 1-methyl-1,2-cyclononadiene isomerization reactions under singlet and triplet direct or sensitized irradiation. Extremely efficient decay occurs from the first singlet excited state to the ground state through at least three different conical intersections (surface crossings). The first of these crossing points is accessed by a one-bond ring closure. From this conical intersection point (CI-A or CI-C), some possible subsequent ground-state reaction paths have been identified: 1) intramolecular C--H bond insertion to form the bicyclic photoproduct and 2) intramolecular C--H bond insertion to form tricyclic photoproducts. An excited state [1,3]-sigmatropic shift leads to the second conical intersection (CI-B or CI-E), which can give a three-bond cyclononyne species. Besides these, in the singlet photochemical reactions of 1-methyl-1,2-cyclononadiene, excited-state, one allenic C--H bond insertion leads to a third conical intersection (CI-D). Possible ground-state reaction pathways from this structure lead to the formation of a diene photoproduct or to transannular insertion photoproducts. Moreover, in the case of triplet 1,2-cyclononadiene and 1-methyl-1,2-cyclononadiene photoisomerization reactions, both chemical reactions will adopt a 1,3-biradical (T(1)/S(0)-1, T(1)/S(0)-2, and T(1)/S(0)-3), which may undergo intersystem crossings leading to the formation of tricyclic or bicyclic photoproducts. The results obtained allow a number of predictions to be made.
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