Electron Flow Characterization of Charge Transfer for Carbonic Acid to Strong Base Proton Transfer in Aqueous Solution

Protonation of the strong base methylamine CH₃NH₂ by carbonic acid H₂CO₃ in aqueous solution, HOCOOH···NH₂CH₃ → HOCOO^–···⁺HNH₂CH₃, has been previously studied (J. Phys. Chem. B 2016, 109, 2271−2280; J. Phys. Chem. B 2016, 109, 2281–2290) via Car–Parinnello molecular dynamics. This proton transfer (PT) reaction within a hydrogen (H)-bonded complex was found to be barrierless and very rapid, with key reaction coordinates comprising the proton coordinate, the H-bond separation R_ON, and a solvent coordinate, reflecting the water solvent rearrangement involved in the neutral to ion pair conversion. In the present work, the reaction’s charge flow aspects are analyzed in detail, especially a description via Mulliken charge transfer for PT (MCTPT). A natural bond orbital analysis and some extensions of them are employed for the complex’s electronic structure during the reaction trajectories. Results demonstrate that consistent with the MCTPT picture, the charge transfer (CT) occurs from a methylamine base nonbonding orbital to a carbonic acid antibonding orbital. A complementary MCTPT reaction product perspective of CT from the antibonding orbital of the HN⁺ moiety to the nonbonding orbital of the oxygen in the H-bond complex is also presented. σ_OH and σ_HN⁺ bond order expressions show this CT to occur within the H-bond OHN triad, an aspect key for simultaneous bond-breaking and -forming in the PT reaction.