title: Probing the Structure of Salt Water under Confinement with First-Principles Molecular Dynamics and Theoretical X-ray Absorption Spectroscopy.
abstract: We investigated the structure of liquid water around cations (Na(+)) and anions (Cl(-)) confined inside of a (19,0) carbon nanotube with first-principles molecular dynamics and theoretical X-ray absorption spectroscopy (XAS). We found that the ions preferentially reside near the interface between the nanotube and the liquid. Upon confinement, the XAS signal of water molecules surrounding Na(+) exhibits enhanced pre-edge and reduced post-edge features with respect to that of pure water, at variance with the solvation shell of Na(+) in bulk water. Conversely, the first solvation shell of confined Cl(-) has a main-edge intensity comparable to that of bulk solvated Cl(-), likely as a result of a high number of acceptor hydrogen bonds in the first solvation shell. Confined nonsolvating water molecules exhibit bulk-like or water-monomer-like properties, depending on whether they belong to core or interfacial layers, respectively.
authors: †Department of Chemistry, Stanford University, 333 Campus Drive, Mudd Building Room 121, Stanford, California 94305, United States.
authors: Heather J
authors: HJ
authors: Kulik
authors: ‡Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, 7000 East Avenue, PO Box 808, L-415, Livermore, California 94550, United States.
authors: Eric
authors: E
authors: Schwegler
authors: ¶Departments of Chemistry and Physics, University of California-Davis, One Shields Avenue, Davis, California 95618, United States.
authors: Giulia
authors: G
authors: Galli
keywords: X-ray absorption spectroscopy; carbon nanotubes; confined water; density functional theory; interfaces; ion solvation