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This structure is best described as a pyramidal complex between singlet methylene and a side\u2010on hydrogen molecule with C<jats:sub><jats:italic>s<\/jats:italic><\/jats:sub> symmetry. At the single reference CI level, it lies 105 kcal\/mol above the methane T<jats:sub><jats:italic>d<\/jats:italic><\/jats:sub>\u2010ground state but is stable relative to dissociation into CH<jats:sub>2<\/jats:sub>(<jats:sup>1<\/jats:sup>A<jats:sub>1<\/jats:sub>) and H<jats:sub>2<\/jats:sub> by 13 kcal\/mol at 0 K (with harmonic zero point energy (ZPE) corrections for all structures). Dissociation of the transition state into triplet methylene and hydrogen also is endothermic (by 4 kcal\/mol), but single bond rupture to give CH<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/tex2gif-stack-1.gif\" xlink:title=\"urn:x-wiley:01928651:media:JCC540160208:tex2gif-stack-1\"\/> and H<jats:sup>.<\/jats:sup> is 3 kcal\/mol exothermic. Thus, it does not appear likely that methane can undergo stereomutation classically beneath the dissociation limit. Confirming earlier conclusions, side\u2010on insertion of <jats:sup>1<\/jats:sup>A<jats:sub>1<\/jats:sub> CH<jats:sub>2<\/jats:sub> into H<jats:sub>2<\/jats:sub> in a perpendicular geometry occurs without activation energy. Planar (D<jats:sub>4<jats:italic>h<\/jats:italic><\/jats:sub>) methane (130.5 kcal\/mol) has four imaginary frequencies. Two of these are degenerate and lead to equivalent planar C<jats:sub>2<jats:italic>v<\/jats:italic><\/jats:sub> structures with one three\u2010center, two\u2010electron bond and two two\u2010electron bonds and two imaginary frequencies. The remaining imaginary frequencies of the D<jats:sub>4<jats:italic>h<\/jats:italic><\/jats:sub> form lead to tetrahedral (T<jats:sub><jats:italic>d<\/jats:italic><\/jats:sub>) and pyramidal (C<jats:sub>4<jats:italic>v<\/jats:italic><\/jats:sub>) methane. The latter has three negative eigenvalues in the force\u2010constant matrix; one of these leads to the T<jats:sub><jats:italic>d<\/jats:italic><\/jats:sub> global minimum and the other to the C<jats:sub><jats:italic>s<\/jats:italic><\/jats:sub> (parallel) stereomutation transition structure. Multireference CI calculations with a large atomic natural orbitals basis set produce similar results, with the electronic energy of the C<jats:sub><jats:italic>s<\/jats:italic><\/jats:sub> stereomutation transition state 0.7 \u00b1 0.5 kcal\/mol higher than that of CH<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/tex2gif-stack-2.gif\" xlink:title=\"urn:x-wiley:01928651:media:JCC540160208:tex2gif-stack-2\"\/> + H<jats:sup>.<\/jats:sup> dissociation products, and a ZPE\u2010corrected energy which is 5 \u00b1 1 kcal\/mol higher. Also considered are photochemical pathways for stereomutation and the possible effects of nuclear spin, inversion tunneling, and the parity\u2010violating weak nuclear interaction on the possibility of an experimental detection of stereomutation in methane. \u00a9 1995 by John Wiley &amp; Sons, Inc.<\/jats:p>","DOI":"10.1002\/jcc.540160208","type":"journal-article","created":{"date-parts":[[2005,1,2]],"date-time":"2005-01-02T01:08:12Z","timestamp":1104628092000},"page":"207-225","source":"Crossref","is-referenced-by-count":90,"title":["Is the stereomutation of methane possible?"],"prefix":"10.1002","volume":"16","author":[{"given":"Melanie J. 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