The contributions of molecular and fragment ions toward the disparate self-chemical ionization (SCI) of ␣-pinene and camphene isomers were investigated. A kinetic model was ␣ constructed to predict the SCI outcomes for these two C 10 H 16 isomers. A major portion of the camphene molecular ions (isolated 500 ms after the 10 ms EI event at 24 eV) unimolecularly dissociated within 200 s of the ionization event. Conversely, under similar experimental conditions, the ␣-pinene molecular ions as well as the major fragment ions of ␣ ␣-pinene and ␣ camphene showed no unimolecular dissociation. The ␣-pinene and camphene molecular ions ␣ yielded product ions through two different reaction mechanisms (direct charge-transfer {CT} and indirect proton transfer {PT}). The isolated terpene fragment ions at m/z 93 and 121 reacted with their respective neutrals to produce [M ϩ H] ϩ . Proton affinity (PA) bracketing experiments, PA additivity schemes, and alkene PA versus adiabatic ionization energy (IE) linear correlation indicated that the PAs of camphene and ␣-pinene were comparable ( ␣ ϳ210 Ϯ 2 kcal · mol Ϫ1 ). The observed [M ϩ H] ϩ SCI terpene ions were mainly the products of various fragment ion reactions. (J Am Soc Mass