Understanding ion specific effects on the solution properties of association colloids is a major unsolved problem, and we are studying the chemistry of gemini surfactants in the vas-phase by mass spectrometry and density functional theory (DFT) to probe ion specific effects in the absence of water. Products from gas-phase fragmentation chemistry of dication-monoanion pairs, M2+X-, of C16H33(CH3)(2)N+-(CH2)(n)-N+(CH3)(2)C16H33 center dot 2X(-) gemini surfactants were determined by using sequential collision induced dissociation mass spectrometry. The spacer length "n" was systematically varied (n = 2, 3, 4, and 6) for each counterion investigated (X- = F-, Br-, Cl-, I-, NO3-, CF3CO2-, and PF6-). The M2+X- pairs fragment into monocationic products from competing E2 and S(N)2 pathways that are readily quantified by tandem MS. The dominant reaction pathway depends on dication and anion structure because it switches from E2 to S(N)2 with decreasing anion basicity and increasing spacer length. For spacer lengths n = 4 and 6, the major S(N)2 product shifts from attack at methylene to methyl on the quaternary ammonium group. DFT calculations of gemini headgroup model bolaform salts, CH3(CH3)(2)N+-(CH2)(n)-N+(CH3)(2)CH3 center dot 2X(-) (X- = F-, Cl-, Br-, and I-, n = 2-4), primarily of activation enthalpies, Delta H double dagger, but also of free energies and entropies for the dication-monoanion pairs, M2+X-, provide qualitative explanations for the MS structure-reactivity patterns. Delta H double dagger values for S(N)2 reactions are independent of X- type and spacer length, while E2 reactions show a significant increase in Delta H double dagger with decreasing anion basicity and a modest increase with spacer length. Comparisons with the Delta H double dagger values of model CH3CH2(CH3)(3)N+X- halides show that the second charge on the dicationic ion pairs does not significantly affect Delta H double dagger and that the change in distance between the nucleophile and leaving group in the ground and transition states structures in S(N)2 reactions is approximately constant indicating that Delta H double dagger governed primarily by electrostatic interactions.