Proton transfers in a number of systems are investigated using ab initio molecular orbital methods. Calculations are carried out with several different basis sets ranging in size from 4–31G to 6–311G**. Electron correlation is included using Møller–Plesset (MP) perturbation theory to second and third orders. Enlargements of the basis set invariably lead to higher energy barriers to proton transfer, while substantial reductions result from inclusion of correlation effects. Application to (HOHOH)− of third-order MP theory with a triple-valence basis set augmented by polarization functions on oxygens and the central proton, denoted MP3/6–311G*(*), leads to excellent agreement with the results of Roos et al. whose calculations involved an extensive CI treatment with a large basis set. For equivalent hydrogen bond lengths, the transfer barrier in the cation (H2OHOH2)+ is nearly identical to that for the (HOHOH)− anion while the barrier in (H3NHNH3)+ is somewhat smaller. The reduction of the SCF barrier height resulting from inclusion of correlation is greater for (O2H3)− than for the above cations. The lowest energy structure of (O2H5)+ contains a symmetric hydrogen bond in which the proton is located midway between the two oxygens whereas asymmetric H bonds are found in the equilibrium geometries of (N2H7)+ and (S2H5)+. The difference in energy between the symmetric and asymmetric configurations of (O2H3)− is extremely small.