Many important bimolecular hydrogen-transfer processes that take place in the atmosphere proceed via a potential energy minimum (hydrogen-bonded complex) that precedes along the minimum energy path the unique saddle point of the reaction, the one corresponding to the hydrogen transfer. It is clear that the one-step low-pressure rate constant of such a reaction does not depend on the existence of any complex along the minimum energy path below the reactant if the reaction takes place by thermal activation over a transition state that lies quite above the reactants (for instance 10 kcal/mol). However, we have quantitatively shown in this article that the scenario notoriously changes if the reaction involves significant tunneling. In this work, we have theoretically calculated the rate constants and their temperature dependence for the reaction HO+HOH→HOH+OH by means of a canonical variational transition state theory and a canonical unified statistical theory (when necessary). Multidimensional tunneling effects have been included with a semiclassical transmission coefficient. Two kinds of modified potential energy surfaces (PESs), obtained from an original ab initio potential energy surface, previously calculated by us, have been used. The Eckart-modified PESs serve to model the hydrogen-abstraction profiles with no complexes along the path, while the Gaussian-modified PESs model the energy profiles with two complexes along the path symmetrically distributed at each side of the abstraction saddle point. Our results show that the existence of those complexes reduces the thickness of the classically forbidden region for energies below the adiabatic barrier, and then tunneling is promoted and the reaction is accelerated. The effect of the complex formation in several kinetic magnitudes, as the Arrhenius parameters and the kinetic isotope effect has also been analyzed. © 1999 John Wiley & Sons, Inc. J Comput Chem 20: 1685–1692, 1999