Sensitivity of charge transfer reactions to hydrocarbon ion structures

Charge transfer reactivities of hydrocarbon ions have been measured with time‐of‐flight techniques, and results correlated with theoretical structures computed by self‐consistent field molecular orbital methods. Recombination energies, ion structures, heats of formation, reaction energetics and relative charge transfer cross‐sections are presented for molecular and fragment ions produced by electron bombardment ionization of CH 4 , C 2 H 4 , C 2 H 6 , C 3 H 8 and C 4 H 10 molecules. Even‐electron bridged cations have low ion recombination energies and relatively low charge transfer cross‐sections as compared with odd‐electron hydrocarbon cations.