Ab initio calculations establish that CH 3 O + CHCH 3 (1) rearranges in gas phase isolation to CH 2 O + C 2 H 5 (2) directly rather than through CH 3 OCH 2 CH 2 + (3). The reaction is predicted to be antarafacial, in accord with the Woodward–Hoffmann (W–H) predictions. We predict an activation energy of 212.0 kJ/mol for this process at the QCISD(T)/6-311G∗∗//MP2/6-311G∗∗ level. We also reinvestigated the degenerate rearrangement of CH 3 OCH 2 + by a 1,3-sigmatropic shift. The W–H model is not a good one for the transition state (TS) for the latter reaction because the π bonding has been completely broken off. That TS is stabilized by three-center bonding between the carbons and the hydrogen being transferred. We also examined the questions of the importance of polarization functions on hydrogen and a set of outer valence functions on all the atoms in describing these hydrogen transfer TSs, and whether it is necessary to include these functions in the TS optimization runs. For the rearrangements we studied, polarization functions on hydrogen are crucial only for 1,2 hydrogen shifts. The 6-31G∗ basis set is adequate and good for the optimization of TSs of other ring sizes. For the 1,3 and 1,4 shifts we examined, a combination of both outer valence functions and polarization functions on hydrogen causes reductions in the computed activation energies ranging from 5.9 kJ/mol for the 1,4 shift at the RHF level to 15.6 kJ/mol for the 1,3 shift at the MP2 level.