Microscopic description of acid–base equilibrium

Abstract

Acid-base reactions are ubiquitous in nature. Understanding their mechanisms is crucial in many fields, from biochemistry to industrial catalysis. Unfortunately, experiments give only limited information without much insight into the molecular behavior. Atomistic simulations could complement experiments and shed precious light on microscopic mechanisms. The large free-energy barriers connected to proton dissociation, however, make the use of enhanced sampling methods mandatory. Here we perform an ab initio molecular dynamics (MD) simulation and enhance sampling with the help of metadynamics. This has been made possible by the introduction of descriptors or collective variables (CVs) that are based on a conceptually different outlook on acid-base equilibria. We test successfully our approach on three different aqueous solutions of acetic acid, ammonia, and bicarbonate. These are representative of acid, basic, and amphoteric behavior.