In present letter the adiabatic approximation is applied to the intramolecular vibrational redistribution (IVR) of water clusters. The isotope, blocking and cluster-size effects are investigated. This letter also examines the assumption associated with the transition state theory applied to unimolecular reactions; that is, IVR is assumed to be completed before the reaction takes place. For this purpose, we choose to study (H2O)(2)H+ -> H2O+ H3O+, and (H2O)(2) -> 2H(2)O processes. In molecular clusters, the vibrational excitation energy transfer between different normal modes has been observed. This will also be investigated for the deuterated species of (HOD)(2)H+. (C) 2013 Elsevier B.V. All rights reserved.