Reaction of Cr + , Mn + , Fe + , Co + , and Ni + with O2 and N2O. Examination of the translational energy dependence of the cross sections of endothermic reactions

Abstract

Reactions of Cr + , Mn + , Fe + , Co + , and Ni + with O2 and N2O to yield metal oxide ions are examined using an ion beam apparatus. Reaction cross sections sigma as a function of ion translational energy E are reported. With one exception, Fe + +N2O, the cross sections exhibit an energy threshold Eo. Several models are used to interpret the excitation functions for the O2 reactions and it is concluded that the classical line-of-centers form sigma alpha (1–Eo/E) is most useful. Bond energies derived in this manner are D°(CrO + ) = 3.45±0.1 eV, D°(MnO + ) = 2.48±0.1 eV, D°(FeO + ) = 3.01±0.1 eV, D°(CoO + ) = 2.76±0.1 eV, and D°(NiO + ) = 1.95±0.1 eV. Since these bond energies are all greater than D°(N2–O) = 1.7 eV, the observation of energy thresholds for the reactions with N2O are surprising. These results are explained in terms of a qualitative view of the electronic potential energy surfaces involved.