Ground-State Long-Range Proton Transfer Controlled by Proton-Accepting Ability of Hydrogen-Bonded Chains: A Theoretical Study

The ground-state triple proton transfer (GSTPT) reactions in HCOOH complexing with H2O, CH3OH, C2H5OH and mixed water–alcohol molecules were studied by quantum mechanical methods in the gas phase and in heptane. The triple proton transfer in HCOOH–S1–S2 (S1, S2 = H2O, CH3OH, C2H5OH) systems all occurred in an asynchronous but concerted protolysis mechanism. The formation pattern of the hydrogen-bonded chain was important to reduce the barrier height of the proton transfer process. When the hydrogen-bonded chain consisted of two identical CH3OH or C2H5OH molecules in the HCOOH–S1–S2 complexes, the GSTPT barrier height of HCOOH–S1–S2 decreased by more than 2 kcal mol−1 compared to that of HCOOH–H2O–H2O both in the gas phase and in heptane, because CH3OH and C2H5OH had larger proton-accepting abilities than had H2O. When the two solvent molecules in the hydrogen-bonded chain in the HCOOH–S1–S2 complexes were different, the barrier height of the proton transfer process varied depending on the proton-accepting ability (basicity) of the hydrogen-bonded chain. The bigger the proton-accepting ability (basicity) of the hydrogen-bonded chain, the lower the barrier height of the proton transfer process. Mixed bridging solvent molecules could accumulate their proton-accepting abilities and thus speeded up proton transfer. The solvent effect evidently decreased the zero point energy-corrected barrier heights of HCOOH clusters and increased the asynchronicity of the proton transfer, while the proton transfer mechanisms did not change in heptane.