Abstract

A theoretical investigation of the microsolvation effect on proton exchange (PE) between carbonic acid and methylamine (CA-MTA) has been explored by quantum dynamics simulations. The structural, energy, and dynamic properties of the CA-MTA complex with and without an explicit water molecule are elucidated at the molecular level. The reactions from this study have been clarified into different types: single-step PE (SSPE) and stepwise PE (SWPE). Without the water molecule, the SSPE mechanism is hardly found but observable with a low probability of 0.2. In particular, the water molecule interacting through intermolecular hydrogen-bonded network between CA and MTA in CA-MTA-W<inf>in</inf> could affect PE by showing both SSPE and SWPE mechanisms. In addition, the existing water molecule plays the significant role in shortening intermolecular hydrogen bonding interactions within the complex resulting in increasing the probability of PE up to 0.92 especially in CA-MTA-W<inf>out</inf>. Hence, one water molecule could be used to provide reliable results to represent the significant activity that occurs for the proton exchangeability of the CA and MTA complex.