Ab initio metadynamics calculations reveal complex interfacial effects in acetic acid deprotonation dynamics

Abstract

Acid-base reactions play a central role in solution chemistry, with carboxylic acids being particularly important in atmospheric chemical processes. In this work, we harness metadynamics calculations with Born-Oppenheimer molecular dynamics (BOMD) simulations to understand deprotonation dynamics of acetic acid (CH 3 COOH) in both bulk and air-water interfacial environments. Collective variables are carefully chosen in our well-tempered metadynamics simulations to capture the deprotonation process in various aqueous configurations. Our findings show that the free energy barrier for deprotonation of acetic acid at the air-water interface is lower than in the bulk, in accordance with the available experimental data. Furthermore, our well-tempered metadynamics calculations suggest that the variations in free energy are primarily due to intricate solvation shell effects. File list (2) download file view on ChemRxiv acetic_acid_dissociation.pdf (1.37 MiB) download file view on ChemRxiv Supplementary_Material.pdf (1.19 MiB)

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