Abstract

The effects of vibrational excitation of reagent ions and collision energy on the proton and charge transfer reactions of H2+ and D2+ with N2, CO, and O2 have been investigated using a method combining photoionization and a radio frequency guided ion technique. For proton transfer the H2++N2 results are quite similar to the H2++Ar system; proton and charge transfer channels are closely coupled for kinetic energies above 3 eV. In contrast, for H2++CO, the vibrational dependence of proton transfer is quite weak. For the H2++O2 case, evidence is seen for direct competition between the charge and proton transfer process. A simple model for charge transfer is used to assess the importance of energy resonance and Franck–Condon effects. In these simple molecular systems, the energy defect is found to be most important to charge exchange, although Franck–Condon factors play a substantial role.

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