Gas-Phase External Solvation of Protonated Benzonitrile by Eight Methanol Molecules.

The gas-phase sequential association of methanol onto protonated benzonitrile (CHCNH) and the proton-bound dimer (CHCN)H have been examined experimentally by equilibrium thermochemical measurements and computationally by density functional theory (DFT). The bonding enthalpy (Δ°) for the association of methanol with protonated benzonitrile (25.2 kcal mol) reflects the strong electrostatic interaction provided by the formation of an ionic hydrogen bond in the CHCNHOHCH cluster in excellent agreement with a DFT-calculated binding energy of 24.

Water-Assisted Proton Transfer in the Sequential Hydration of Benzonitrile Radical Cation CHCN(HO): Transition to Hydrated Distonic Cation CHCNH(HO) with ≥ 4.

The stepwise hydration of the benzonitrile radical cation with one-seven HO molecules was investigated experimentally and computationally with density functional theory in CHCN(HO) clusters. The stepwise binding energies (Δ) were determined by equilibrium measurements for CHCN(HO) and for CHCNH(HO) with = 5, 6, and 7 to be 8.8 and 11.