A systematic experimental and theoretical investigation of the influence of reactant energy on the reactivity Of (V2O5)(n=1,2)(+) clusters with ethylene (Justes, D. R.; Mitric, R.; Moore, N. A.; Bonacic-Koutecky, V.; Castleman, A. W., Jr. J. Am. Chem. Soc., 2003, 125, 6289)(1) provided evidence of the rate controlling steps in the reaction. Herein, we present further experimental and theoretical evidence for our recently proposed radical cation mechanism for oxygen atom transfer from (V2O5)=(+)(1,2) clusters to ethylene. In particular the results of ab initio molecular dynamics simulations are found to further support the radical cation mechanism. Experimental reaction cross sections at the zero pressure limit and rate coefficients show that the energy dependence of the reaction cross section is in accord with the Langevin formula. Evidence is presented that ion-molecule association is the rate determining step, whereas subsequent hydrogen transfer and formation of acetaldehyde proceed without significant barriers. We propose a kinetic model for the reaction cross section that fully accounts for the experimental findings. The model offers the prospect of elucidating the details of the general reaction mechanisms through a study of the energy dependence of the reaction cross sections.