Paper detail

A microscopic description of acid-base equilibrium

Acid-base reactions are ubiquitous in nature. Understanding their mechanisms is crucial in many fields, from biochemistry to industrial catalysis. Unfortunately, experiments only give limited information without much insight into the molecular behaviour. 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 methadynamics. This has been made possible by the introduction of novel descriptors or collective variables (CVs) that are based on a conceptually new 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 behaviour.