AN AB INITIO MOLECULAR DYNAMICS STUDY ON THE SOLVATION OF FORMATE ION AND FORMIC ACID IN WATER

Abstract

Formate ion and formic acid are linked in water by the equilibrium for the acidic dissociation of formic acid, which as the simplest carboxylic acid is an important model system. In this study, the microscopic details of the solvation around a formate ion and around a formic acid molecule in aqueous solution are explored by ab initio molecular dynamics simulations, at 300, 500, 700, and 900 K. The formate ion exerts a strong influence on the surrounding solvent molecules by hydrogen bonding, which restricts the access of other water molecules. With rising temperature, the hydrogen bonds are disrupted, and the space around formic acid becomes more accessible. Solvation of the formic acid is marked by its partial dissociation to produce a proton, and the hydrogen bond interaction around a formic acid is not as strong as that around a formate ion. The acidic dissociation becomes less favorable as temperature rises, which indicates a lesser catalytic role for the water molecules in the thermal dissociation of formic acid.