Nuclear Quantum Effects in Hydrophobic Nanoconfinement.

Buddha Ratna Shrestha, Sreekiran Pillai, Adriano Santana, Stephen H Donaldson, Tod A Pascal, Himanshu Mishra

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

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.
Original languageEnglish (US)
Pages (from-to)5530-5535
Number of pages6
JournalThe Journal of Physical Chemistry Letters
Volume10
Issue number18
DOIs
StatePublished - Jul 31 2019

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