Recombination of Autodissociated Water Ions in a Nanoscale Pure Water Droplet

Abstract

The recombination of water ions has diverse scientific and practical implications, ranging from acid–base chemistry and biological systems to planetary environments and applications in fuel cell and carbon conversion technologies. While spatial confinement affects the physicochemical properties of water dynamics, its impact on the recombination process has rarely been studied. In this work, we investigate the dynamics of water, the water ion distribution, and the ion recombination process in water droplets as a function of droplet size through molecular dynamics simulations and adaptive quantum mechanical/molecular mechanical calculations. We compare the dynamics of recombination in water droplet sizes ranging from 100 to 18 000 waters, both in their interiors and on their surfaces. We found that the self-diffusion of water dramatically decreases in droplets with a diameter below 2.2 nm. Using a classical RexPoN force-field, we found that the ions in 1000 H₂O’s spend almost 50% of the time on the surface and 0.5 nm beneath it with a slight preference for OH^– ion to reside longer on the surface. We estimate that, on average, recombination in these drops occurs at 400 ps in 1000 H₂O’s and 1 ns in 3000 H₂O’s. We also found that recombination is not limited by the local structure of the surface or the size of the droplet but can be influenced by the geometry of the water wire connecting the ions as they approach each other, which can often prevent recombination. Our results provide insights to the reaction microenvironments presented by nanoscopic water droplets.