Alkylperoxy and hydroperoxyalkyl radicals are key reactive intermediates in hydrocarbon oxidation mechanisms. An understanding of the interconversion of these two species via a hydrogen migration reaction is of fundamental importance to the prediction of chain branching reactions and end product composition. An extensive ab initio investigation of the hydrogen migration reaction in 1-ethyl, 1-propyl, 1-butyl, 1-pentyl, and 1-hexylperoxy radicals is conducted to assess the validity of using cycloalkanes to model the ring strain of their transition states as well as the effect of both location of the migrating hydrogen and directionality of the remaining alkyl chain in the transition state of the reaction involving a secondary hydrogen. The G2 and CBS-Q composite methods are used to determine the activation energy and enthalpy of reaction relative to the alkylperoxy radical. Both methods show good agreement with five experimentally determined reaction enthalpies, having root mean squared deviations of 0.7 and 1.3 kcal mol(-1) for the CBS-Q and G2 methods, respectively. The effect of hydrogen abstraction site and transition state geometry, particularly axial and equatorial geometries of the remaining alkyl chain, on the activation energy, Arrhenius A-factor, tunneling, and rate coefficient are discussed. Differences between terminal adjacent and nonterminal adjacent secondary sites result in small but consistent differences in barrier height. Failure of key assumptions within the cycloalkane based estimation method leads to the break clown in the accuracy for both small and large transition states. For large transition states, the breakdown of these assumptions also results in the failure of the current cycloalkane method as a conceptual model. Of great interest is the observed alteration in the preferred H-migration from the 1,5 to the 1,6 H-migration within the temperature region where these reactions are particularly important to the combustion mechanism.