Nuclear Quantum Effects in Hydrophobic Nanoconfinement

Nuclear quantum effects (NQEs) in water arise due to delocalization, zero-point energy (ZPE), and quantum tunneling of protons. Whereas quantum tunneling is significant only at low temperatures, proton delocalization and ZPE influence the properties of water at normal temperature and pressure (NTP), giving rise to isotope effects. However, the consequences of NQEs for interfaces of water with hydrophobic media, such as perfluorocarbons, have remained largely unexplored. Here, we reveal the existence and signature of NQEs modulating hydrophobic surface forces at NTP. Our experiments demonstrate that the attractive hydrophobic forces between molecularly smooth and rigid perfluorinated surfaces in nanoconfinement are ≈10% higher in H₂O than in D₂O, even though the contact angles of H₂O and D₂O on these surfaces are indistinguishable. Our molecular dynamics simulations show that the underlying cause of the difference includes the destabilizing effect of ZPE on the librational motions of interfacial H₂O, which experiences larger quantum effects than D₂O.