Abstract
The least-motion insertion reaction of singlet methylene into molecular hydrogen is forbidden in the sense of Woodward and Hoffmann and has been predicted to involve a barrier height of approximately 27 kcal/mol. Here ab initio electronic structure theory has been applied to the non-least-motion features of the same potential energy surface. A double zeta basis set of contracted Gaussian functions was used in conjunction with moderately large (2120 configurations) configuration interaction (CI) techniques. For an initial C/sub s/ point group approach theory predicts no barrir or activation energy at all. This result is illustrated with the aid of contour maps showing several cuts through the potential energy hypersurface. It is also noted that the single determinant self-consistent field (SCF) method does not properly describe several of the main features of this concerted non-least-motion pathway.
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