Nuclear quantum effects in fullerene–fullerene aggregation in water

Abstract

We studied the effects of the quantum delocalization in space of the hydrogen atoms of water in the aggregation process of two fullerene molecules. We considered a case using a purely repulsive water–fullerene interaction, as such a situation has shown that water-mediated effects play a key role in the aggregation process. This study becomes feasible, at a reduced computational price, by combining the path integral (PI) molecular dynamics (MD) method with a recently developed open-system MD technique. Specifically, only the mandatory solvation shell of the two fullerene molecules was considered at full quantum resolution, while the rest of the system was represented as a mean-field macroscopic reservoir of particles and energy. Our results showed that the quantum nature of the hydrogen atoms leads to a sizable difference in the curve of the free energy of aggregation; that is, that nuclear quantum effects play a relevant role.